CN103962159A - Photocatalyst and preparation method and application thereof - Google Patents
Photocatalyst and preparation method and application thereof Download PDFInfo
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- CN103962159A CN103962159A CN201410204187.7A CN201410204187A CN103962159A CN 103962159 A CN103962159 A CN 103962159A CN 201410204187 A CN201410204187 A CN 201410204187A CN 103962159 A CN103962159 A CN 103962159A
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Abstract
The invention discloses a photocatalyst and a preparation method and application thereof. The photocatalyst is a metal composite which is formed by compounding 99.99-98 percent by weight of metal oxide and 0.01-2 percent by weight of metal sulfide. The metal oxide is zinc oxide or titanium oxide, and the metal sulfide is molybdenum sulfide or tungsten sulfide. The preparation method of the photocatalyst comprises the following steps: stirring and mixing the metal oxide and the metal sulfide, performing ultrasonic treatment on the mixture and drying to obtain the photocatalyst. The photocatalyst can realize absorption of light of all wave bands of sunlight, improve the photoelectric conversion efficiency and inhibit carrier recombination at the same time, thereby comprehensively improving the photocatalytic efficiency. The photocatalyst has higher catalytic efficiency and higher catalytic speed on decomposed products compared with other photocatalysts. The photocatalyst is relatively full and comprehensive in the utilization of sunlight. In addition, the catalyst has the characteristics of low cost and easy availability.
Description
Technical field
The present invention relates to field of environment protection, relate in particular to a kind of photochemical catalyst and its preparation method and application.
Background technology
Problem of environmental pollution, as one of difficult problem of the world today, is subject to increasing attention, efficient, safety, addresses this problem and enjoys popular confidence cheaply.The mechanism of action of himself excellence of photocatalysis meets above-mentioned requirements completely, and unique requirement is exactly that we need to prepare the photochemical catalyst with efficient catalytic performance and the efficiency of light energy utilization.But mainly contain TiO for light-catalysed material both at home and abroad at present
2have benefited from the features such as the good and bio-compatibility of its cheapness, physico-chemical property is good, become a kind of photocatalyst material of natural excellence, but only account for 5% of sunshine because the broad stopband of its 3.2eV makes its light that can only absorb ultraviolet band, greatly reduce the utilization to sunshine.Another kind of in recent years also generally application in photocatalysis be zinc oxide its but to have multiple nanostructured energy gap be that 3.37eV exists and TiO
2outside same problem, zinc oxide has again fast light corrosivity poor as photochemical catalyst, and environment pH value is required to the shortcomings such as harsh, mainly by being the conventional means addressing the above problem to its doping and finishing to adjust its band structure, to improve its performance.
The metal oxide of nanostructured has large specific area, suitable energy gap, be easy to the excellent specific property of the aspects such as preparation and enjoy high praise, but self exists again some drawbacks.The molybdenum bisuphide of two-dimensional structure has excellent and many performances Graphene as a kind of two-dimensional structure of novel class Graphene simultaneously, its block structure from a band gap is to the straight band gap monoatomic layer structure with 2.83eV energy gap, greatly strengthens it to the utilization of sunshine especially visible wavelength.And because the energy gap of the molybdenum bisuphide of varying number layer changes slightly, the molybdenum bisuphide of varying number layer is mixed make it have like this and absorb the energy gap that all sunshine wave bands match, thereby realize, all band of solar energy is absorbed, thereby by improving to a great extent, the utilization of solar energy is improved to light-catalysed efficiency like this.The prepared composite photo-catalyst of perfect adaptation of these two kinds of materials will have very high catalytic performance.
With regard to preparation method, chemical vapour deposition technique is to prepare one of the most frequently used method of nano structural material, and this method has degree of crystallinity and the feature such as getting property is good compared with additive method.While liquid phase stripping method prepares individual layer or which floor molybdenum bisuphide of minority is more conducive to realize quantification with respect to additive method, and the molybdenum bisuphide of its gained has various layer, and preparation process is very simple, cheapness.
The present invention is intended to which floor molybdenum bisuphide simple composite of monoatomic layer prepared by the Zinc oxide nano sheet of high-quality standby CVD legal system and liquid phase stripping method or minority, thereby prepares efficient photochemical catalyst, realizes the efficient utilization to sunshine.
Chinese patent (CN 103464180) discloses just preparation method and the application thereof of material of a kind of novel photocatalysis.By compound to Graphene and P25, utilize the excellent electrical conductivity performance of Graphene to promote the photo-generated carrier migration of P25, reach electronics and separate with the efficient of hole, thus the ultraviolet catalytic performance of lifting P25.Subsequently, utilizing the method for surface chlorination that compound is goed deep into modification, introduce chlorine radical, is that degradation property further promotes.
Chinese patent (CN1472007A) discloses sulfuric acid and titanium dioxide composite photocatalyst, there is visible light activity, can be by the excited by visible light of wavelength 387-510 nanometer, improve the activity of Ti4+, catch the ability of light induced electron, and surface hydroxyl or oxygen anion free radical are caught photohole, thereby reduce the right recombination rate in light induced electron hole, improved organic contamination degradation effect.
Above two patents are the formula that discloses composite photo-catalyst, but this composite photo-catalyst to light utilize little i.e. most light, light induced electron and the holes that can only absorb ultraviolet region of wave-length coverage easily compound, need the shortcoming and defect of noble metal as aspects such as co-catalysts.
Summary of the invention
One of object of the present invention be for solve above-mentioned composite photo-catalyst to light utilize little i.e. most light, light induced electron and the holes that can only absorb ultraviolet region of wave-length coverage easily compound, need noble metal to provide one can utilize all band sunshine as the shortcoming and defect of the aspects such as co-catalyst, postpone photo-generated carrier compound p-n junction and just can realize fast the photochemical catalyst to organic degraded without any need for other co-catalysts fast.
Two of object of the present invention is the preparation method of a kind of photochemical catalyst that provides above-mentioned.
Technical scheme of the present invention
A kind of photochemical catalyst, for metal oxide and metal sulfide are calculated by mass percentage, i.e. metal oxide: metal sulfide is 99.99%-98%:0.01%-2%, the ratio that is preferably 99.99%-99%:0.01%-1% carry out compound and must metal composite;
Described metal oxide is zinc oxide or titanium oxide;
Described metal sulfide is molybdenum sulfide or tungsten sulfide;
Described metal oxide is random nano-sheet structure, and described nano-sheet structure is of a size of 10-900nm, and thickness is 10-50nm;
Described metal sulfide is random nano-sheet structure, and described nano-sheet structure is of a size of 10-100nm, and thickness is 0.6-5nm.
The preparation method of above-mentioned a kind of photochemical catalyst, concrete steps are as follows:
By metal oxide and metal sulfide, after stirring 10-60min and mixing, controlled frequency is that 100-200W carries out ultrasonic 30-90min, then control temperature 100-150 DEG C dry, obtain described photochemical catalyst;
Wherein metal oxide can be prepared by methods such as chemical vapour deposition technique, hydro-thermal method, pulsed laser deposition or molecular beam epitaxies, and the present invention preferentially selects chemical vapour deposition technique;
Described chemical vapour deposition technique, to plate silicon chip or the Al of noble metal
2o
3for substrate, the carbon dust that the metal oxide powder that is 99.99% by purity and purity are 99.99% in mass ratio 1:10-10:1 mixes, and mixes 2.5%-25% phosphorus pentoxide (P
2o
5);
The control parameter of above-mentioned chemical vapour deposition technique process is as follows: growth temperature is 800-1000 DEG C, and growth time is less than 10min, 40 DEG C/min of programming rate, argon gas (Ar) flow 10-120sccm, oxygen (O
2) flow 10-80sccm.
Metal sulfide wherein can be inserted the methods such as stripping method, liquid phase stripping method, chemical vapour deposition technique or hydro-thermal method and be produced by mechanical stripping method, electrochemical lithium ion, and the present invention preferentially selects the ultrasonic stripping method of liquid phase.
Which floor the preparation of metal sulfide of monoatomic layer or minority:
Adopt the liquid phase ultrasonic method of peeling off to prepare required metal sulfide, first choose solution that lamina block metal sulfide is had to a fine suspension effect and prepare which floor metal sulfide of monoatomic layer or minority as 1-METHYLPYRROLIDONE (NMP), NVP (NVP), hydrogen phosphide cumene (CHP) or water etc. are used as liquid phase carrier;
The metallic sulfide powder that is 99.99% by purity is placed in liquid phase carrier, wherein the concentration of metal sulfide is 0.01-1g/mL, then carry out ultrasonic peeling off, after ultrasonic peeling off, controlling centrifugal speed is that 1500-12000r/min carries out centrifugal 30-60min, obtain photochemical catalyst, the metal composite that metal oxide and metal sulfide are composited.
Above-mentioned ultrasonic stripping process control parameter is: ultrasonic time 30-800min, supersonic frequency 80-500W.
Above-mentioned a kind of photochemical catalyst is for the photocatalytic degradation of organic matter methylene blue, and the ratio that its consumption is 1:100 in the mass ratio of photochemical catalyst and methylene blue is calculated.
Useful technique effect of the present invention
Owing to having selected two kinds, to be well suited for for the material of photochemical catalyst be that metal oxide and metal sulfide and its have after compound and be suitable for carrying out light-catalysed energy gap to photochemical catalyst of the present invention, therefore can realize and can improve again its electricity conversion to the absorption of sunshine all band light after both are compound, can also delay the compound of carrier, comprehensive raising photocatalysis efficiency simultaneously.
Further, photochemical catalyst of the present invention, than the photochemical catalyst of other types, has higher catalytic efficiency and catalysis speed faster to methylene blue.Secondly this kind of catalyst is more abundant to the utilization rate of sunshine, more comprehensively.
Further, photochemical catalyst of the present invention, due to selected material be metal oxide and metal sulfide be all common and widely used metallic compound therefore raw material be easy to get, and production cost is low.
Further, photochemical catalyst of the present invention, its preparation technology is simple, all has good catalytic effect under Uv and visible light, can effectively adapt to large-scale industrial production and can be applied in large-scale water treatment technology.
Further, photochemical catalyst of the present invention, because metal oxide and metal sulfide are all almost therefore to have huge specific area in two-dimentional structure, and adding less and catalytic effect is high, and stable chemical nature, can be effectively compatible in any one advanced treatment process of existing water treatment, and described two kinds of compositions of photochemical catalyst of the present invention are all water insoluble, the rate of recovery is high, has huge environment protection significance and value.
In sum, photochemical catalyst of the present invention, has higher catalytic efficiency and catalysis speed faster than the photochemical catalyst of other types to analyte.Utilization rate to sunshine is more abundant, more comprehensively.The feature that this photochemical catalyst also has cheapness, is easy to get in addition.
Brief description of the drawings
Fig. 1, ZnO-MoS
2the SEM figure of the ESEM of composite photo-catalyst;
Fig. 2, ZnO-MoS
2the TEM figure of the transmission electron microscope of composite photo-catalyst under 790000X multiplying power;
Fig. 3, ZnO-MoS
2tEM diffraction pattern under the transmission electron microscope of composite photo-catalyst under 200X multiplying power;
Fig. 4, ZnO-MoS
2the XPS figure of the x-ray photoelectron power spectrum of composite photo-catalyst;
Fig. 5, ZnO-MoS
2the absorption curve of composite photo-catalyst, pure ZnO, P25 pressed powder;
Fig. 6, Zn-MoS
2the photoelectric current curve of composite photo-catalyst, pure ZnO, P25 pressed powder;
Fig. 7, ZnO-MoS
2the absorption curve of composite photocatalyst for degrading methylene blue;
Fig. 8, ZnO-MoS
2the degradation curve of the degradation of methylene blue of composite photo-catalyst and pure ZnO and P25 pressed powder;
Fig. 9, ZnO-MoS
2the kinetics calculated curve of the degradation of methylene blue of composite photo-catalyst and pure ZnO and P25 pressed powder;
Figure 10, ZnO-MoS
2the bar graph of the degradation of methylene blue of composite photo-catalyst and pure ZnO and P25 pressed powder;
Figure 11, ZnO-MoS
2the organic schematic diagram of composite photocatalyst for degrading.
Detailed description of the invention
Also by reference to the accompanying drawings the present invention is further set forth below by specific embodiment, but do not limit the present invention.
embodiment 1
A kind of photochemical catalyst, for metal oxide and metal sulfide are calculated by mass percentage, i.e. metal oxide: the ratio that metal sulfide is 99%:1% is carried out the compound metal composite obtaining;
Described metal oxide is zinc oxide;
Described metal sulfide is molybdenum bisuphide;
Described zinc oxide is random nano-sheet structure, and its nano-sheet structure is of a size of 10-900nm, and thickness is 10-50nm;
Described molybdenum bisuphide is random nano-sheet structure, and its nano-sheet structure is of a size of 10-100nm, and thickness is 0.6-5nm.
The preparation method of above-mentioned photochemical catalyst, specifically comprises the steps:
1, adopt traditional chemical vapour deposition technique to prepare Zinc oxide nano sheet
(1), by etc. Zinc oxide powder and the graphite powder of mass ratio fully grind, then add 5% phosphorus pentoxide, then pack in quartz boat;
(2), the Al of Au film will be coated with
2o
3substrate is placed on quartz boat powder, and quartz boat is placed in quartz glass;
(3), quartz boat glass tube is put into tube furnace, and make quartz boat aim at stove centre;
(4), be warming up to 1000 DEG C, heating rate is 40 DEG C/min;
(5), pass into argon gas (Ar) flow 10 Sccm, oxygen (O
2) flow 30Sccm, growth time 5min;
(6) keep aeration status, until naturally cool to room temperature, always;
(7), on substrate, whiteness is Zinc oxide nano sheet;
2, adopt liquid phase stripping method to prepare monoatomic layer molybdenum bisuphide
(1), molybdenum disulfide powder is added to NVP (NVP), its concentration is 0.05g/ml, and mixture is placed in to brown vial;
(2), brown vial be placed in to ultrasonic wave carry out ultrasonicly, frequency is 400W, ultrasonic time 400min, and keep ultrasonic temperature below 15 DEG C;
(3), ultrasonic complete mixed liquor be placed in to centrifuge tube carry out centrifugally, centrifugal speed is 11000r/min, centrifugation time 60min;
(4), the supernatant of centrifuge tube top 1ml is taken out;
(5), the supernatant of taking-up is placed in after beaker deionized water is repeatedly diluted, cleaned and is dried,, until NVP (NVP) is removed completely, just can obtain high-quality monoatomic layer molybdenum bisuphide;
Wherein in centrifugal rear supernatant, the amount of monoatomic layer molybdenum bisuphide can be undertaken quantitatively by thermogravimetric analysis (TGA);
3, the preparation of composite photo-catalyst
Step 1 metal oxide and step 2 metal sulfide are stirred after 30min mixing, and controlled frequency is that 200W carries out ultrasonic 30min, then controls 100 DEG C of dry 24h of temperature, obtains photochemical catalyst, i.e. ZnO-MoS
2composite photo-catalyst.
The ZnO-MoS of above-mentioned gained
2the pattern of composite photo-catalyst adopts SEM (manufacturer: FEI, model: Quanta FEG) scan, the SEM of gained schemes as shown in Figure 1, can observe large stretch of irregular and very thin Zinc oxide nano sheet from Fig. 1, on Zinc oxide nano sheet, trickling down some almost molybdenum bisuphide of transparent monoatomic layer, as the part of black circles in Fig. 1, from Fig. 1, can observe Zinc oxide nano sheet and there is large area and very thin, and the almost transparent molybdenum sulfide being scattered is thereon very even, has large specific area.
The ZnO-MoS of above-mentioned gained
2the appearance structure of composite photo-catalyst adopts transmission electron microscope (manufacturer: TESEQ, model: D-TEM) scan, the TEM of gained schemes as shown in Figure 2 and Figure 3, from the TEM figure of Fig. 2 and Fig. 3, be further confirmed, the existence of seeing zinc oxide and molybdenum bisuphide that can be very cheer and bright and be all monocrystalline, crystallization effect is very good.
The ZnO-MoS of above-mentioned gained
2the element of composite photo-catalyst adopts x-ray photoelectron power spectrum (manufacturer: Kratos company of Britain, model: XSAM 800) analyze, the XPS of gained schemes as shown in Figure 4, the existence of the molybdenum bisuphide from the XPS figure of Fig. 4 in the photochemical catalyst of proving again gained of the present invention.
embodiment 2
A kind of photochemical catalyst, for metal oxide and metal sulfide are calculated by mass percentage, i.e. metal oxide: the ratio that metal sulfide is 99.9%:0.1% is carried out the compound metal composite obtaining;
For the composite construction of metal oxide and metal sulfide, a kind of photochemical catalyst, for the composite construction of metal oxide and metal sulfide, pressing the sulfuration of metal oxide and metal 99.9% mixes in mass ratio, stir 30 minutes, ultrasonic 30 minutes, power was 200W, 100 DEG C of baking temperatures, time 24h gets final product to obtain described photochemical catalyst;
Described metal oxide is zinc oxide;
Described metal sulfide is molybdenum bisuphide;
Described zinc oxide is random nano-sheet structure, and its nano-sheet structure is of a size of 10-900nm, and thickness is 10-50nm;
Described molybdenum bisuphide is random nano-sheet structure, and its nano-sheet structure is of a size of 10-100nm, and thickness is 0.6-5nm.
The preparation method of above-mentioned a kind of photochemical catalyst, with embodiment 1.
embodiment 3
A kind of photochemical catalyst, for metal oxide and metal sulfide are calculated by mass percentage, i.e. metal oxide: metal sulfide is that 99.99%:0.01% carries out the compound metal composite obtaining;
Described metal oxide is zinc oxide;
Described metal sulfide is molybdenum bisuphide;
Described zinc oxide is random nano-sheet structure, and its nano-sheet structure is of a size of 10-900nm, and thickness is 10-50nm;
Described molybdenum bisuphide is random nano-sheet structure, and its nano-sheet structure is of a size of 10-100nm, and thickness is 0.6-5nm.
The preparation method of above-mentioned a kind of photochemical catalyst, with embodiment 1.
The ZnO-MoS of above-described embodiment 1-3 gained
2composite photo-catalyst and pure ZnO and P25 pressed powder utilize ultraviolet-visual spectrometer (manufacturer: Shimadzu company at ambient temperature, model: Shimadzu UV-2600) measured to the absorption curve of light as shown in Figure 5, as can be seen from Figure 5 relatively pure ZnO and P25, the ZnO-MoS of this experiment gained
2composite photo-catalyst is strengthened greatly to the absorption of light, this not only shows visible region is also shown to the light to ultraviolet light region, show that thus described composite photo-catalyst is improving remarkably productive aspect the light absorption of sunshine all band, when this raising to its photocatalysis efficiency very favorable.
The ZnO-MoS of above-described embodiment 1-3 gained
2composite photo-catalyst and pure ZnO and P25 pressed powder utilize probe station (manufacturer: U.S. Cascade Microtch at ambient temperature, model: M150) the photoelectric current curve that records is as shown in Figure 6, as can be seen from Figure 6 with respect to pure ZnO and P25, the ZnO-MoS of this experiment gained
2composite photo-catalyst photoelectricity flow valuve under illumination obviously increases, and is 3-4 times of P25, shows that thus described composite photo-catalyst has improved its electricity conversion to a certain extent.
application Example the photocatalysis experiment of photochemical catalyst
Get the ZnO-MoS of gained in embodiment 1-3
2composite photo-catalyst is respectively used to the photocatalytic degradation of organic matter methylene blue, and concrete steps are as follows:
(1), get respectively the ZnO-MoS of 40mg above-described embodiment 1-3 gained
2composite photo-catalyst, the pure ZnO of 40mg and 40mg P25 pressed powder are placed in beaker, and adding respectively 40ml concentration is in 10mg/L aqueous solution of methylene blue;
(2), above-mentioned beaker is first placed in to darkroom 10min, gets 5ml and be placed in centrifuge tube, and then dislocation under sunshine, (light rate density is 1800uV/cm
2), magnetic agitation, samples every 2min;
(3), centrifuge tube is centrifugal, centrifugal speed is 8000r/min, centrifugal 15min;
(4) centrifugal complete supernatant is placed in to ultraviolet-visible spectrophotometer, because the characteristic absorption peak of methylenum careuleum is at 664nm place, therefore observe herein the variation of its light absorption value.
The ZnO-MoS of above-described embodiment 2 gained
2absorption curve after composite photocatalyst for degrading methylene blue as shown in Figure 7, as can be seen from Figure 7 under solar light irradiation, after 2min, there is 90% methylene blue to be degraded, after 4 minutes, methylene blue is degradable, has shown that thus composite catalyst has good catalytic effect.
The ZnO-MoS of above-described embodiment 1-3 gained
2degradation curve after composite photo-catalyst and pure ZnO and P25 pressed powder degradation of methylene blue as shown in Figure 8, as can be seen from Figure 8 adds MoS
2znO degradation of methylene blue is produced to certain influence, along with MoS later
2the degradation rate of the increase methylene blue of amount, by accelerating gradually, is still worked as MoS
2amount reach certain value and restrict on the contrary its reduction of speed rate later, this is mainly because of because too much MoS
2can hinder the absorption of composite catalyst to light, thereby reduce catalytic efficiency, show thus to add appropriate MoS
2the photocatalysis efficiency of ZnO is had to significant enhancing effect.
The ZnO-MoS of above-described embodiment 1-3 gained
2kinetics calculated curve after composite photo-catalyst, pure ZnO, P25 pressed powder degradation of methylene blue and bar graph respectively as Fig. 9 and as shown in figure 10, have further proved appropriate MoS
2to the raising of ZnO photocatalysis efficiency.
In sum, the compound photochemical catalyst of the Zinc oxide nano sheet of gained and monoatomic layer molybdenum bisuphide has outstanding extinction ability with respect to pure ZnO and P25 pressed powder, the ability of photo-generated carrier and the well ability of photocatalysis to degrade organic matter.
Photochemical catalyst of the present invention only describes as an example of the photochemical catalyst of metal oxide zinc oxide and the compound gained of metal sulfide molybdenum bisuphide example, but does not limit the composite photo-catalyst of other metal oxides and metal sulfide gained.
Further, can find out by the schematic diagram of the photochemical catalyst reaction in Figure 11, in the time that photon energy absorbs the irradiation semiconductor of codomain higher than semiconductor, semi-conductive valence band electronics generation band-to-band transition.Transit to conduction band from valence band, thereby produce electronics (e
-) and hole (h
+), the dissolved oxygen trapped electron that is now adsorbed on nano grain surface forms superoxide anion, and the hydroxide ion and the water that are adsorbed on catalyst surface are oxidized to hydroxyl free radical by hole.And superoxide anion and hydroxyl free radical have very strong oxidisability, can be by most oxidation operations to end product CO
2and H
2o, even also can thoroughly decompose some inorganic matters, thereby has further confirmed employing ZnO and MoS
2compound gained photochemical catalyst adopts this principle to decompose organic matter.
Described in summary, photochemical catalyst of the present invention can be realized and can improve again its electricity conversion to the absorption of sunshine all band light, can also delay the compound of carrier, comprehensive raising photocatalysis efficiency simultaneously.
Above said content is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (6)
1. a photochemical catalyst, is characterized in that described photochemical catalyst is that metal oxide and metal sulfide are calculated by mass percentage, i.e. metal oxide: the ratio that metal sulfide is 99.99%-98%:0.01%-2% is carried out the compound metal composite obtaining;
Described metal oxide is zinc oxide or titanium oxide;
Described metal sulfide is molybdenum sulfide or tungsten sulfide;
Described metal oxide is random nano-sheet structure, and described nano-sheet structure is of a size of 10-900nm, and thickness is 10-50nm;
Described metal sulfide is random nano-sheet structure, and described nano-sheet structure is of a size of 10-100nm, and thickness is 0.6-5nm.
2. photochemical catalyst as claimed in claim 1, it is characterized in that described photochemical catalyst is that metal oxide and metal sulfide are calculated by mass percentage, i.e. metal oxide: the ratio that metal sulfide is 99.99%-99%:0.01%-1% is carried out the compound metal composite obtaining;
Described metal oxide is zinc oxide;
Described metal sulfide is molybdenum sulfide.
3. the preparation method of a kind of photochemical catalyst as claimed in claim 1 or 2, is characterized in that concrete steps are as follows:
By metal oxide and metal sulfide, after stirring 10-60min and mixing, controlled frequency is that 100-200W carries out ultrasonic 30-90min, then control temperature 100-150 DEG C dry, obtain described photochemical catalyst;
Wherein chemical vapour deposition technique, hydro-thermal method, pulsed laser deposition or the preparation of molecular beam epitaxy method for metal oxide;
Metal sulfide wherein adopts mechanical stripping method, electrochemical lithium ion to insert stripping method, the ultrasonic stripping method of liquid phase, chemical vapour deposition technique or hydro-thermal method preparation.
4. the preparation method of a kind of photochemical catalyst as claimed in claim 3, the chemical vapour deposition technique described in it is characterized in that is prepared metal oxide, to plate silicon chip or the Al of noble metal
2o
3for substrate, the carbon dust that the metal oxide powder that is 99.99% by purity and purity are 99.99% in mass ratio 1:10-10:1 mixes, and the phosphorus pentoxide that mixes 2.5%-25% carries out chemical vapour deposition (CVD);
The control parameter of above-mentioned chemical vapour deposition technique process is as follows: growth temperature is 800-1000 DEG C, and growth time is less than 10min, 40 DEG C/min of programming rate, argon flow amount 10-120sccm, oxygen flow 10-80sccm.
5. the preparation method of a kind of photochemical catalyst as claimed in claim 3, the ultrasonic stripping method of liquid phase described in it is characterized in that is prepared metal sulfide, first chooses 1-METHYLPYRROLIDONE, NVP, hydrogen phosphide cumene or water as liquid phase carrier;
Then the metallic sulfide powder that is 99.99% by purity is placed in liquid phase carrier, wherein the concentration of metal sulfide is 0.01-1g/mL, then carry out ultrasonic peeling off, after ultrasonic peeling off, controlling centrifugal speed is that 1500-12000r/min carries out centrifugal 30-60min, obtain photochemical catalyst, the metal composite that metal oxide and metal sulfide are composited;
Above-mentioned ultrasonic stripping process control parameter is: ultrasonic time 30-800min, supersonic frequency 80-500W.
6. photochemical catalyst as claimed in claim 1 or 2 is for the photocatalytic degradation of organic matter methylene blue, and the ratio that its consumption is 1:100 in the mass ratio of photochemical catalyst and methylene blue is calculated.
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| CN106964368A (en) * | 2017-03-21 | 2017-07-21 | 山东科技大学 | A kind of molybdenum sulfide nanometer sheet/titanium dioxide nanoplate/graphite fiber composite materials and preparation method thereof |
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