CN108176393A - A kind of orderly, high density Ag-Al2O3-MoS2The preparation method of nanostructured - Google Patents
A kind of orderly, high density Ag-Al2O3-MoS2The preparation method of nanostructured Download PDFInfo
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- CN108176393A CN108176393A CN201711445920.4A CN201711445920A CN108176393A CN 108176393 A CN108176393 A CN 108176393A CN 201711445920 A CN201711445920 A CN 201711445920A CN 108176393 A CN108176393 A CN 108176393A
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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
- B01J23/16—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
- B01J23/28—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention is a kind of orderly, high density Ag Al2O3‑MoS2The preparation method of nanostructured.This method prepares individual layer molybdenum disulfide by chemical vapour deposition technique in common optical glass on piece；In one layer of silver nanoparticle film of electric anodic oxidation aluminium formwork surface hot evaporation of preparation, it is then placed in heat preservation in atomic layer deposition chamber and forms silver nano-grain and be embedded in the alumina formwork hole of ordered arrangement, form orderly, highdensity silver nanoparticle ball array；Vaporous precursors are passed through, one layer of Al is deposited on silver nano-grain surface2O3Film obtains Ag Al2O3Core-shell nanospheres array structure；Gained sample is taken out, individual layer molybdenum disulfide is transferred to the Ag Al of preparation by way of wet method transfer2O3On core-shell nanospheres array structure, and used supporting layer polystyrene (PS) when shifting is removed using toluene solution, to form orderly, high density Ag Al2O3‑MoS2Nanostructured, and tested applied to Photocatalyzed Hydrogen Production.
Description
Technical field
The present invention relates to field of nano material preparation and photocatalysis field more particularly to a kind of orderly, high density Ag-
Al2O3-MoS2The preparation method of nanostructured.
Background technology
From the point of view of current global energy is using pattern, fossil fuel still occupies leading position, but due to fossil fuel
Be difficult to regenerate in short time and use during the gases such as carbon dioxide, oxynitrides that generate, weather for the earth and
Environment produces influence difficult to the appraisal.It is each for how providing convenience, cleaning and the efficient energy for ever-increasing population
State needs the big problem solved.Therefore such as solar energy, water energy, the wind energy sustainability energy are increasingly becoming alternative fossil
The selection of fuel.However, it is a major challenge that various countries currently face that energy above, which is stored, and is integrated into power grid.Hydrogen has
Very high energy density since its combustion product only has water, is typically considered a kind of perfect clean energy resource carrier.Pass through light
The mode of electrochemical decomposition water, it is very promising mode to convert solar energy into chemical energy, however, to make decomposition water into
This reduction, great technological break-through are necessary, it is critical that develop height in abundant material from the earth
The catalytic component of activity, high stability.
In currently known material, platinum and platinum metal are the highest catalyst of evolving hydrogen reaction efficiency, but its resource has
Sex-limited and high cost limits its commercial applications.In view of tight demand of the whole world for the energy at present, searches out one
Cheap alternative of the kind with high catalytic activity, status of the platinum in liberation of hydrogen catalyst to be replaced to be very necessary.Recently, it receives
Rice structure molybdenum disulfide because free energy and the platinum of its sulphur edge constraint hydrogen atom very close to having been identified as platinum group catalyst
Potential substitute, however finiteness and bad luck of the catalytic hydrogen evolution performance of simple molybdenum disulfide due to active number of edge points
Electric conductivity and be restricted.
The surface plasma body resonant vibration (SPR) quickly grown in recent years is the phenomenon that photochemical catalyst efficiency is overcome to be restricted
Provide a good chance.Photochemical catalyst starts redox reaction by using photo-generated carrier (electrons and holes),
Realize solar energy to chemical conversion of energy.The coinage metals such as metal nanoparticle, particularly gold, silver, copper in visible light region and
The feature localized surface plasmons resonance (LSPR) that near visible region generates helps to improve in photocatalytic process pair can
See the light absorption in light and near visible region, the energy of plasma of generation is passed through into simultaneous plasma-induced resonance
The mode of energy transfer (PIRET) and Direct electron transfer (DET), from nano metal ion-transfer to semiconductor in, and half
Electron-hole pair is generated on conductor, the efficiency of photochemical catalyst is improved and generates Beneficial Effect.It is current to have silver-colored (Ag) nanometer of high density
The preparation of ball array and preparation Ag-Al2O3- Ag nanometer nuclear shell nano-structures are applied to surface Raman enhancement scattering (SERS) field
Related patent and article, mainly using anodised aluminium made from electrochemical erosion method as template, by sputtering Ag metals to mould
On plate, in addition herein in connection with technique for atomic layer deposition on silver deposition of aluminium oxide, but by this high density Ag nanospheres and Ag-
Al2O3- Ag nanometer nuclear shell nano-structures are applied to Photocatalyzed Hydrogen Production as working electrode and can directly be contacted in the presence of silver with acid solution,
Under the conditions of alive, blackening is easily aoxidized, damages working electrode, and there are the undesirable limitations of catalytic effect.
Invention content
The purpose of the present invention is for deficiency existing for current techniques, provides a kind of orderly, high density Ag-Al2O3-MoS2
The preparation method of nanostructured.This method is directly using common optical glass as substrate, respectively with molybdenum trioxide (MoO3) and simple substance
Sulphur is molybdenum source and sulphur source, grows individual layer molybdenum disulfide in the above, and be transferred into preparation by the method that wet method shifts
High density, orderly Ag-Al2O3One kind, which is obtained, in nano-core-shell structure, after removing transfer supporting layer can be applied to photocatalysis hydrogen production
The working electrode in field.
The technical scheme is that：
A kind of orderly, high density Ag-Al2O3-MoS2The preparation method of nanostructured, the method includes：
Individual layer molybdenum disulfide is prepared in common optical glass on piece by chemical vapor deposition (CVD) method；In electrochemistry corruption
Hot evaporation one layer of silver nanoparticle film in anodic oxidation aluminium formwork surface prepared by erosion method；Gained sample is put into atomic layer deposition chamber
It is heated to preset temperature and is kept for 3 hours, make Ag films solid-state dehumidification to form silver nano-grain and be embedded in ordered arrangement
In alumina formwork hole, orderly, highdensity silver nanoparticle ball array is formed；Vaporous precursors are passed through under institute's preset temperature,
One layer of Al is deposited on silver nano-grain surface2O3Film obtains Ag-Al2O3Core-shell nanospheres array structure；Gained sample is taken out,
Using individual layer molybdenum disulfide prepared by chemical vapor deposition (CVD) method Ag-Al will be transferred to by way of wet method transfer2O3Core
On shell nanosphere array structure, and used supporting layer polystyrene (PS) when shifting is removed using toluene solution, to be formed
Orderly, high density Ag-Al2O3-MoS2Nanostructured；And it is tested applied to Photocatalyzed Hydrogen Production.
(1) individual layer molybdenum disulfide is prepared in common optical glass on piece by chemical vapor deposition (CVD) method, it is spare；Its
In, the condition of growth individual layer molybdenum disulfide is 3~5mg of molybdenum source, and 0.4~0.6g of sulphur source, temperature is 650~800 DEG C, growth time
2~10min, molybdenum source and sulphur source distance are 30~50cm, and gas of carrier gas is argon gas (Ar), gas of carrier gas flow velocity for 10~
100sccm, the molybdenum disulfide 4.2 × 10 grown on every 3.75 square centimeters of sheet glass-4~1.2 × 10-3mg；
(2) aluminium flake is corroded by electrochemical method, using aluminium flake as anode, platinum electrode is cathode, applies voltage
25~40 volts, electrolyte is 0.4~0.6mol/L oxalic acid solutions, the reaction time for 12~for 24 hours, obtain anodic oxidation aluminium formwork；
Then the template is put into supersonic cleaning machine and carries out ultrasound clearly using deionized water, acetone, ethyl alcohol, deionized water successively
It washes；Wherein, ultrasonic power is 150~200W, and frequency 40KHz, ultrasonic time is 3~5 minutes respectively；
(3) sample tray being fixed on anodic oxidation aluminium formwork obtained in the previous step in high vacuum thermal evaporation coating system
On, positioned at the surface of tungsten boat, silver granuel is placed in tungsten boat, electrified regulation is to 980~1050 DEG C, until silver is melted into liquid in boat
Body, one layer of Ag films of hot evaporation；Wherein, thermal evaporation intracavitary pressure is evacuated to 3~5 × 10-4Pa, the rate of thermal evaporation areSample stage velocity of rotation is 10~50r/min, and the thickness of metal Ag films is 15~40nm；
(4) and then the anodic oxidation aluminium formwork after hot evaporation silver atomic layer deposition intracavitary is put into, and 150~250
2~4h is kept the temperature at DEG C；
(5) after carrying out heat preservation arrival setting time, start to be passed through vaporous precursors, trimethyl aluminium to atomic layer deposition intracavitary
With water respectively as silicon source and oxygen source, one layer of Al is deposited on silver nano-grain surface by pulse cycle2O3Film obtains Ag-
Al2O3Core-shell nanospheres array structure, including：Running parameter during using atomic layer deposition apparatus is：Temperature is 150~250
DEG C, 133~399Pa of pressure, cycle-index 30~60 times, the burst length of trimethyl aluminium is set as 0.001~0.005s, water
Burst length is set as 0.0001~0.0005s；
(6) the individual layer molybdenum disulfide prepared in step (1) is transferred to Ag-Al by way of wet method transfer2O3Nucleocapsid is received
On rice spherical array array structure, and transfer supporting layer polystyrene (PS) is removed using toluene solution, obtain Ag-Al2O3-MoS2Nanometer
Structure.
Orderly, the high density Ag-Al2O3-MoS2The application of nano structural material is used it for preparing photocatalysis production
The working electrode of hydrogen.
Beneficial effects of the present invention are：
The embodiment of the present invention is proposed prepares orderly, high density Ag-Al in anodic oxidation aluminium substrate2O3-MoS2Nano junction
Structure：Utilize the orderly of anodic oxidation aluminium formwork, the hole of high density distribution so that the Ag films after solid-state dehumidification become ping-pong ball edge
In hole, the nanometer ball array being accordingly distributed is formed；Atomic layer deposition (ALD) technology is recycled in metal Nano silver grain
(Ag-NPs) surface and gap location uniformly deposit one layer of very thin Al2O3Nano thin-film forms Ag-Al2O3Spherical core-shell nano
Structure；The individual layer molybdenum disulfide for chemical vapor deposition (CVD) method being used to prepare on common optical glass is shifted by wet method
Mode be transferred to Ag-Al2O3On core-shell nanospheres array structure, and used support when shifting is removed using toluene solution
Ag-Al is made in strata styrene (PS)2O3-MoS2Working electrode.It is embodied as：
(1) individual layer MoS is grown directly on common optical glass by chemical vapour deposition technique2, with traditional Si/SiO2、
Sapphire substrates compare, and achieve the effect that reduce cost；(2) preparation process is simple, can large area prepare, by hot evaporation and
Atomic layer deposition method can once prepare the Ag-Al of diameter 4cm sizes2O3Substrate can be cut by required size as transfer
Substrate；(3) high density of preparation, orderly Ag-Al2O3-MoS2Nanostructured is compared with simple molybdenum disulfide, identical
Under the conditions of illumination simulation, the voltage (starting voltage) in -10mA is reduced to -290mV from -500mV, reduces 210mV；Separately
Current density during external -600mV is from 30.2mA/cm-2Increase to 72.5mA/cm-2, increase 2.4 times.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is a kind of orderly, high density Ag-Al of the embodiment of the present invention2O3-MoS2The preparation method and application of nanostructured
In light-catalyzed reaction flow chart；
Fig. 2 be application example of the present invention orderly, high density Ag-Al2O3-MoS2Nanostructured prepares schematic diagram；
Fig. 3 is the scanning electron microscope that application example of the present invention prepares individual layer molybdenum disulfide by chemical vapor deposition (CVD) method
Scheme, scale is 20 μm in figure；
Fig. 4 is the scanning electron microscope (SEM) photograph of the anodic oxidation aluminium formwork pores array used in application example of the present invention, scale in figure
For 200nm；
Fig. 5 is the SEM of the one layer of silver nanoparticle film figures that application example of the present invention is deposited in anodized aluminum surfaces, and thickness is about
For 25nm, scale is 200nm in figure；
Fig. 6 is having of being formed after one layer of silver nanoparticle Thin-film anneal of application example anodized aluminum surfaces of the present invention deposition
The SEM of sequence silver nanoparticle ball array schemes, and scale is 200nm in figure；
Fig. 7 is that the method for application example atomic layer deposition of the present invention deposits one layer of Al on orderly silver nanoparticle ball surface2O3,
The Ag-Al of formation2O3The SEM of nucleocapsid schemes, and scale is 200nm in figure；
Fig. 8 is that individual layer molybdenum disulfide is transferred to Ag-Al by application example of the present invention with wet method transfer method2O3Nucleocapsid
On orderly, the high density Ag-Al that are formed2O3-MoS2The SEM of nanostructured schemes, and scale is 1 μm in figure；
Fig. 9 is application example Ag-Al of the present invention2O3The TEM of orderly nucleocapsid schemes, and scale is 5nm in figure；
Figure 10 is application example glass-carbon electrode of the present invention (GC provides electric conductivity as substrate, do not have catalytic activity), two
Molybdenum sulfide/GC, Ag-Al2O3-MoS2For electrode under the conditions of identical simulation solar irradiation, obtained electrochemistry linear scans volt-ampere
(lsv) curve graph, abscissa are the potential of opposite reversible hydrogen electrode (RHE), and ordinate is corresponding current density.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work
Embodiment shall fall within the protection scope of the present invention.
Metallic silver is formed using solid-state dehumidification (solid state dewetting) directly on anodic oxidation aluminium formwork to receive
Rice corpuscles, Nano silver grain can be embedded in the hole of template, so as to form corresponding with form plate hole orderly, large area, height
The metal nano particles array of density.This simple method prepares orderly, highdensity array structure for low cost, large area
Provide possibility.Therefore it is proposed that preparing orderly, high density Ag-Al in anodic oxidation aluminium formwork substrate2O3-MoS2Nanometer
Structure.Nano silver grain (Ag-NPs) surface formed after annealing using atomic layer deposition (ALD) technology uniformly deposits one
The very thin Al of layer2O3Nano thin-film forms orderly, high density Ag-Al2O3Spherical nanometer nuclear shell nano-structure.It again will be in ordinary optical glass
On glass Ag-Al is transferred to by way of wet method transfer with individual layer molybdenum disulfide prepared by chemical vapor deposition (CVD) method2O3Core
On shell nanosphere array structure, and transfer supporting layer polystyrene (PS) is removed, Ag-Al is made2O3-MoS2Working electrode, and should
It is tested for Photocatalyzed Hydrogen Production.
Invention is to provide a kind of combination chemical vapor deposition (CVD) method, atomic layer deposition (ALD) technique and thermal evaporation plating
Membrane technology prepares a kind of Ag-Al with photocatalysis Decomposition water effect2O3-MoS2Nanostructured.This method preparation process is simple,
Uniformity is good, can large area preparation.
As shown in Figure 1, for a kind of orderly, high density Ag-Al of the embodiment of the present invention2O3-MoS2The preparation method of nanostructured
Flow chart, the method includes：
101st, individual layer molybdenum disulfide (MoS is prepared on common optical glass by chemical vapour deposition technique2), it is spare；
102nd, anodic oxidation aluminium formwork is prepared and in one layer of silver nanoparticle film of template surface hot evaporation；
103rd, gained sample is put into atomic layer deposition chamber and is heated to preset temperature, form Ag films solid-state dehumidification
Silver nano-grain is simultaneously embedded in the hole of template, forms orderly, highdensity silver nanoparticle ball array；Lead under institute's preset temperature
Enter vaporous precursors, trimethyl aluminium and water respectively as silicon source and oxygen source, one layer of Al is deposited on silver nano-grain surface2O3Film,
Obtain Ag-Al2O3Core-shell nanospheres array structure；
104th, the individual layer molybdenum disulfide prepared on common optical glass is transferred to Ag- by way of wet method transfer again
Al2O3On core-shell nanospheres array structure, and transfer supporting layer PS is removed to get Ag-Al2O3-MoS2Nanostructured；
105th, by the Ag-Al of preparation2O3-MoS2Nanostructured is used for the working electrode of Photocatalyzed Hydrogen Production, by applying electricity
Pressure observes its starting voltage and generates the situation of electric current.
Preferably, in the step 101, the condition of growth individual layer molybdenum disulfide is molybdenum source 3mg, sulphur source 0.5g, sheet glass
Size for 1.5cm × 2.5cm, temperature is 750 DEG C, growth time 3min, and molybdenum source is 30cm with sulphur source distance, is carried
Gas gas is argon gas (Ar), and gas of carrier gas flow velocity is 30sccm, and the molybdenum disulfide quality of growth is calculated as 8.4 × 10-4mg；
Preferably, before the step 102, aluminium flake is corroded by electrochemical method, used aluminium flake purity：
99.999%, brand：Goodfellow, thickness 0.5mm, diameter 40mm, using aluminium flake as anode, platinum electrode is cathode, is immersed
In electrolyte, apply 40 volts of voltage, electrolyte is 0.42mol/L oxalic acid solutions, and the reaction time is for 24 hours；It will using supersonic cleaning machine
Anodised aluminium substrate sample obtained is cleaned by ultrasonic successively with deionized water, acetone, ethyl alcohol, deionized water, ultrasonic work(
Rate is 150W, and frequency 40KHz, ultrasonic time is 5 minutes respectively；
Preferably, it compared with other plated film modes, is used using thermal evaporation deposited metal film in the step 102
The mode plated film of thermal evaporation has the advantages that plated film is uniform, and controllable-rate is prepared simply, and cost is relatively low.In general, hot evaporation
Rate is slower, and the compactness of metallic film is better, and roughness is lower；
Preferably, thermal evaporation intracavitary pressure is evacuated to 3 × 10 in 102-4Pa, the rate of thermal evaporation areSample stage rotates
Speed is 20r/min, and the thickness of metallic film is 25nm；
In the step 103, the Ag films for being deposited on anodic oxidation aluminium formwork at room temperature are in semisteady-state, work as sample
When being heated to certain temperature annealing, the metallic film in half stable state is broken in substrate surface, forms the little particle of nanoscale,
Here it is the processes of solid-state dehumidification, and after solid-state drying, Nano silver grain can be embedded in the hole of template；
Preferably, the annealing temperature used in the step 103 is 250 DEG C, keeps 3h constant at such a temperature, at this point,
The density of the orderly Nano silver grain obtained is about 1x1010A/cm2, pass through the average diameter for the Nano silver grain that template obtains
Between 55~60nm；
Before being deposited in the step 103, need to preset the cyclic process that 2~3 air sources are trimethyl aluminium, to prevent
Only trimethyl aluminium is remained in reaction chamber and gas source pipe；
Preferably, the deposition parameter in the step 103 is set as 250 DEG C of temperature, and pressure control is in 133Pa, cycle time
Number is 40 cycles, and the burst length of trimethyl aluminium is set as 0.001s, and the burst length of water is set as 0.0002s；
In the step 104, wet method transfer process is by hydrogen fluoride (HF) solution by the unformed titanium dioxide of glass surface
Silicon etching falls, and is transferred to the Ag-Al of preparation2O3On core-shell nanospheres array structure, then will shift when used supporting layer is used
Toluene solution removes, and Ag-Al is made2O3-MoS2Working electrode；
Preferably, the etching liquid used in the step 104 wet method transfer process is the fluorination that mass fraction is 15%
Hydrogen (HF) solution, transfer supporting layer are polystyrene (PS)；Polystyrene solution configuration method is that 1gPS is dissolved in 10ml toluene
In solvent；Transfer detailed process is that the PS solution 2~3 being configured is taken to drip, and being equably spin-coated on growth by spin coating instrument has individual layer
On the common optical glass substrate surface of molybdenum disulfide, wherein spin coating rotating speed is 3500r/min, spin-coating time 60s, Zhi Hou
15min is toasted at 85 DEG C；After mass fraction is 15% hydrogen fluoride (HF) solution etches, the PS with molybdenum disulfide is taken off
Transfer supporting layer and the Ag-Al for being transferred to preparation2O3On core-shell nanospheres array structure, 10min, Zhi Houyong are toasted at 60 DEG C
Toluene solution removes PS transfer supporting layers；
Preferably, in step 105 test process, test solution be 0.5mol/L sulfuric acid solutions, scanning range -0.8
~0v, sweep speed 2mv/s, used light source be 500W xenon lamps, electric current 15A.
The embodiment of the present invention is described in detail below in conjunction with application example and Fig. 2-Figure 10：
Embodiment 1
Present embodiments provide it is a kind of based on the technologies such as chemical vapor deposition, hot evaporation and atomic layer deposition prepare orderly,
High density Ag-Al2O3-MoS2The method of working electrode, preparation flow as shown in Fig. 2,
(a) individual layer molybdenum disulfide (MoS is prepared on common optical glass by chemical vapor deposition (CVD) method2), it is standby
With；
(b) electrochemical method prepares anodic oxidation aluminium formwork and in one layer of silver nanoparticle film of template surface hot evaporation；
(c) gained sample is put into atomic layer deposition chamber and is heated to preset temperature, form Ag films solid-state dehumidification
Silver nano-grain is simultaneously embedded in the hole of template, forms orderly, highdensity silver nanoparticle ball array；It is obtained after heat preservation
The density of orderly Nano silver grain is about 1x1010A/cm2, nanometer ping-pong ball its average diameter that can control by template is situated between
Between 55~65nm；Vaporous precursors, trimethyl aluminium and water are passed through under institute's preset temperature respectively as silicon source and oxygen source,
Silver nano-grain surface deposits one layer of Al2O3Film obtains Ag-Al2O3Core-shell nanospheres array structure；
(d) the individual layer molybdenum disulfide of preparation is transferred to Ag-Al by way of wet method transfer2O3Core-shell nano ball array
In structure, and used supporting layer polystyrene (PS) when shifting is removed using toluene solution；
(e) by the Ag-Al of preparation2O3-MoS2Nanostructured is used for the working electrode of Photocatalyzed Hydrogen Production, by applying voltage,
It observes its starting voltage and generates the situation of electric current.
Technical scheme of the present invention is further described below.
Chemical vapor deposition (CVD) method prepares individual layer molybdenum disulfide (MoS on common optical glass2)：Preferably, it grows
The molybdenum source of molybdenum disulfide is molybdenum trioxide (MoO3) 3mg, sulphur source is elemental sulfur (S) 0.5g, and molybdenum source is with sulphur source distance
30cm, substrate are common optical glass piece, and size is 1.5cm × 2.5cm, and growth temperature is 750 DEG C, and gas of carrier gas is argon
Gas (Ar), gas flow rate 30sccm, growth time 3min, the molybdenum disulfide quality of growth are calculated as 8.4 × 10-4mg；
Hot evaporation pre-treatment：Aluminium flake is corroded by electrochemical method, used aluminium flake, purity：99.999%,
Brand：Goodfellow, thickness 0.5mm, diameter 40mm, using aluminium flake as anode, platinum electrode is cathode, is immersed in electrolyte,
Apply 40 volts of voltage, electrolyte is 0.42mol/L oxalic acid solutions, and for 24 hours, anodic oxidation aluminium substrate is made in the reaction time；Using super
Sound cleaning machine carries out anodised aluminium substrate sample obtained ultrasonic clear with deionized water, acetone, ethyl alcohol, deionized water successively
It washes, ultrasonic power 150W, frequency 40KHz, ultrasonic time is 5 minutes respectively；
Hot evaporation metallic film：Anodic oxidation aluminium formwork after previous step is cleaned and dried is fixed on high vacuum thermal evaporation plating
On sample tray in membranous system, positioned at the surface of tungsten boat, silver granuel is placed in tungsten boat, electrified regulation is to 980 DEG C, until in boat
Silver is melted into liquid, and one layer of Ag films of hot evaporation adjust electric current to evaporation rate stabilization and exist at this timeThen sample is adjusted
Pallet rotating speed opens sample baffle after being 20r/min.After it is preferred that, vapor deposition silver film thickness is 25nm；
Ag-Al2O3It is prepared by core-shell nano ball array：In order to avoid ping-pong ball and acid solution are in direct contact, it is also necessary on surface
One layer of aluminum oxide film is covered, and requires that film is uniform and thickness is controllable, therefore, we use atomic layer deposition (ALD) skill
Art plates a thin layer of aluminium oxide in Ag nanometers of ball arrays, forms Ag-Al2O3Nucleocapsid；I.e. by the anode after hot evaporation silver
Alumina formwork is put into atomic layer deposition intracavitary, and 3h is kept the temperature at 250 DEG C, and gas phase forerunner is then passed through under preset temperature
Body, trimethyl aluminium and water are set as 0.001s, the burst length of water respectively as silicon source and oxygen source, the burst length of trimethyl aluminium
0.0002s is set as, one layer of Al is deposited on silver nano-grain surface2O3Film obtains Ag-Al2O3Core-shell nanospheres array junctions
Structure；Preferably, the parameter in atomic layer deposition process is set as 250 DEG C of temperature, pressure control in 133Pa, cycle-index 40 times；
Ag-Al2O3-MoS2It is prepared by nanostructured：By what is grown in common optical glass on piece by chemical vapour deposition technique
Individual layer molybdenum disulfide is transferred to Ag-Al by the method for wet etching2O3In core-shell nano ball array, and removed with toluene solution
Used supporting layer polystyrene (PS) during transfer, it is preferred that the etching used in the step 104 wet method transfer process
Liquid is hydrogen fluoride (HF) solution that mass fraction is 15%, and transfer supporting layer is polystyrene (PS)；Polystyrene solution is configured
1gPS is is dissolved in 10ml toluene solvants by method；Transfer detailed process is that the PS solution 2~3 being configured is taken to drip, and passes through spin coating
Instrument, which is equably spin-coated on growth, to be had on the common optical glass substrate surface of individual layer molybdenum disulfide, wherein spin coating rotating speed 3500r/
Min, spin-coating time 60s toast 15min at 85 DEG C later；It is carved by hydrogen fluoride (HF) solution that mass fraction is 15%
After erosion, take the transfer supporting layers of the PS with molybdenum disulfide off and be transferred to the Ag-Al of preparation2O3On core-shell nanospheres array structure,
10min is toasted at 60 DEG C, removes PS transfer supporting layers with toluene solution later；
Photocatalyzed Hydrogen Production is tested：By the Ag-Al of preparation2O3-MoS2Nanostructured is used for the working electrode of Photocatalyzed Hydrogen Production,
By applying voltage, observing its starting voltage and generating the situation of electric current, it is preferred that in step 105 test process, survey
Examination solution is 0.5mol/L sulfuric acid solutions, and scanning range -0.8~0v, sweep speed 2mv/s, used light source is 500W
Xenon lamp, electric current 15A.
SEM such as Fig. 3-Fig. 9：Fig. 3 be application example of the present invention by chemical vapour deposition technique in common optical glass on piece
Si/SiO is transferred to after growth individual layer molybdenum disulfide2On SEM figures, scale is 20 μm in figure；Fig. 4 is application example institute of the present invention
The SEM of the anodised aluminium groove template used schemes, and scale is 200nm in figure；Fig. 5 is application example hot evaporation 25nm of the present invention
SEM after Ag films schemes, and scale is 200nm in figure；Fig. 6 is to obtain Ag nanometers of spherical arrays after application example Ag films of the present invention are annealed
The SEM of array structure schemes, and scale is 200nm in figure；Fig. 7 is obtained after one layer of aluminium oxide of application example atomic layer deposition of the present invention
Ag-Al2O3The SEM of core-shell nanospheres array structure schemes, and scale is 200nm in figure；Fig. 8 is application example Ag-Al of the present invention2O3-
MoS2The SEM of nanostructured schemes, and scale is 1 μm in figure；Fig. 9 is application example Ag-Al of the present invention2O3Transmit electricity to nucleocapsid
Sub- microscope (TEM) figure, has as can be seen from the figure obtained one layer of quasi-continuous Al after atomic layer deposition2O3Nano thin-film.
Figure 10 is glass-carbon electrode (GC), molybdenum disulfide/GC, Ag-Al2O3-MoS2Under the conditions of identical simulation solar irradiation,
Obtained electrochemistry linear scanning volt-ampere (lsv) curve graph, potential of the abscissa for opposite reversible hydrogen electrode (RHE), ordinate
For corresponding current density, Ag-Al2O3-MoS2Electrode and pure MoS2Electrode compares, and the starting voltage in -10mA reduces
210mV, current density increase 2.4 times in -600mV.
Above-described specific embodiment has carried out the purpose of the present invention, technical solution and advantageous effect further
It is described in detail, it should be understood that the foregoing is merely the specific embodiment of the present invention, is not intended to limit the present invention
Protection domain, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Unaccomplished matter of the present invention is known technology.
Claims (2)
1. a kind of orderly, high density Ag-Al2O3-MoS2The preparation method of nanostructured, it is characterized in that this method includes：
（1）Pass through chemical vapor deposition（CVD）Method prepares individual layer molybdenum disulfide in common optical glass on piece, spare；Wherein, it is raw
The condition of long individual layer molybdenum disulfide is 3 ~ 5mg of molybdenum source, and 0.4 ~ 0.6g of sulphur source, temperature is 650 ~ 800 DEG C, 2 ~ 10min of growth time,
Molybdenum source is 30 ~ 50cm with sulphur source distance, and gas of carrier gas is argon gas（Ar）, gas of carrier gas flow velocity is 10 ~ 100sccm, often
The molybdenum disulfide 4.2 × 10 grown on 3.75 square centimeters of sheet glass-4~1.2×10-3mg；
（2）Aluminium flake is corroded by electrochemical method, using aluminium flake as anode, platinum electrode is cathode, applies voltage 25 ~ 40
Volt, electrolyte are 0.4 ~ 0.6mol/L oxalic acid solutions, the reaction time for 12 ~ for 24 hours, obtain anodic oxidation aluminium formwork；Then should
Template is put into supersonic cleaning machine and is cleaned by ultrasonic successively using deionized water, acetone, ethyl alcohol, deionized water；Wherein, surpass
Acoustical power is 150 ~ 200W, and frequency 40KHz, ultrasonic time is 3 ~ 5 minutes respectively；
（3）Anodic oxidation aluminium formwork obtained in the previous step is fixed on the sample tray in high vacuum thermal evaporation coating system,
Positioned at the surface of tungsten boat, silver granuel is placed in tungsten boat, electrified regulation is to 980 ~ 1050 DEG C, until silver is melted into liquid in boat, heat
One layer of Ag films are deposited；Wherein, thermal evaporation intracavitary pressure is evacuated to 3 ~ 5 × 10-4Pa, the rate of thermal evaporation for 0.1 ~ 0.5/S, sample
Sample platform velocity of rotation is 10 ~ 50r/min, and the thickness of metal Ag films is 15 ~ 40nm；
（4）Then the anodic oxidation aluminium formwork after hot evaporation silver is put into atomic layer deposition intracavitary, and is protected at 150 ~ 250 DEG C
2 ~ 4h of temperature；
（5）After carrying out heat preservation arrival setting time, start to be passed through vaporous precursors, trimethyl aluminium and water to atomic layer deposition intracavitary
Respectively as silicon source and oxygen source, one layer of Al is deposited on silver nano-grain surface by pulse cycle2O3Film obtains Ag-Al2O3
Core-shell nanospheres array structure, including：Running parameter during using atomic layer deposition apparatus is：Temperature is 150 ~ 250 DEG C, pressure
133 ~ 399Pa, cycle-index 30 ~ 60 times, the burst length of trimethyl aluminium are set as 0.001 ~ 0.005s, and the burst length of water sets
It is set to 0.0001 ~ 0.0005s；
（6）By step（1）The individual layer molybdenum disulfide of middle preparation is transferred to Ag-Al by way of wet method transfer2O3Core-shell nanospheres
On array structure, and transfer supporting layer polystyrene is removed using toluene solution（PS）, obtain Ag-Al2O3-MoS2Nanostructured.
2. orderly, high density Ag-Al as described in claim 12O3-MoS2The application of nano structural material is used it for preparing
The working electrode of Photocatalyzed Hydrogen Production.
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