CN109046392A - A kind of catalyst and preparation method thereof of photocatalysis Decomposition aquatic products hydrogen - Google Patents
A kind of catalyst and preparation method thereof of photocatalysis Decomposition aquatic products hydrogen Download PDFInfo
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- CN109046392A CN109046392A CN201811058126.9A CN201811058126A CN109046392A CN 109046392 A CN109046392 A CN 109046392A CN 201811058126 A CN201811058126 A CN 201811058126A CN 109046392 A CN109046392 A CN 109046392A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The present invention relates to the technical fields of photocatalysis Decomposition aquatic products hydrogen, more particularly, to a kind of catalyst and preparation method thereof of photocatalysis Decomposition aquatic products hydrogen.The catalyst of the photocatalysis Decomposition aquatic products hydrogen carries out reduction removing to the molybdenum disulfide array including molybdenum disulfide array nano titania hole array and be grown in the nanometer hole array.The preparation method includes the following steps: to cheat growth in situ molybdenum disulfide array in array in nano titania, and carries out reduction removing to get the catalyst of the photocatalysis Decomposition aquatic products hydrogen.The catalyst of photocatalysis Decomposition aquatic products hydrogen of the present invention, absorbing ability is strong, and light absorption range is wide, and photo-generated carrier activity is high, and Photocatalyzed Hydrogen Production ability is strong；Nonmetallic plasma resonance light absorption is realized on the basis of the Intrinsic Gettering of material, the utilization rate of solar energy is greatly improved, and excellent performance is shown in seawater hydrogen manufacturing.
Description
Technical field
The present invention relates to the technical fields of photocatalysis Decomposition aquatic products hydrogen, more particularly, to a kind of photocatalysis Decomposition aquatic products hydrogen
Catalyst and preparation method thereof.
Background technique
Fossil energy is the highest energy of current dependency degree, but the non-renewable and excessive use of chemical fuel is not only
The problems such as exacerbating the risk of future source of energy, while also bringing air pollution and global warming.Therefore, exploitation cleaning is renewable
New energy it is extremely urgent.Hydrogen energy source is similar with natural gas, has many advantages, such as that pollution-free, abundant raw material, calorific value are high, it is considered to be
Solve one of the energy crisis preferably selection strategy that current mankind is faced.The means for preparing hydrogen have very much, wherein utilizing
Decomposing water with solar energy hydrogen manufacturing and effectively storage are one of ideal, most promising means in Solar use.
Current more common decomposing water with solar energy hydrogen production photocatalyst is mainly semiconductor material, such as TiO2、ZnO、CdS
Deng.Single semiconductor light-catalyst is since energy band is single, the disadvantages of low, catalyst stability that there are hydrogen production efficiencies is poor.In order to
It solves the problem above-mentioned, people pass in succession through the methods of doping, surface modification, building hetero-junctions to improve single semiconductor material
Photocatalytic activity.However, even different knot catalyst processed, it is also difficult to realize all standing that solar energy is composed entirely, catalytic efficiency
It is low.Therefore, the light abstraction width of material, the different band structures of superposition, the energy level for adjusting light induced electron is further widened to remain
Vital goal in research in photocatalysis hydrogen production.
The study found that being extinction position and the phasmon material for reacting position with a series of nano-noble metals (Pt, Au, Pb etc.)
Additional photoresponse can be generated on the basis of the Intrinsic Gettering of basis material, and make generate photoelectron activity compared with
It is high.Meanwhile the noble metal nano array of high-sequential has that stronger surface plasma resonance effect, light absorption be strong, light is urged
It is prominent to change effect.Numerous research all shows that noble metal plasmon Photocatalyzed Hydrogen Production is a kind of efficient production hydrogen technology.But
Be, noble metal it is expensive, increase the cost of manufacture of catalyst.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of catalyst of photocatalysis Decomposition aquatic products hydrogen, to solve in the prior art
Existing catalyst low efficiency and the high technical problem of cost of manufacture.
The second object of the present invention is to provide a kind of preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen, institute
Preparation method simple process and low cost is stated, large-scale production is suitble to, industrial applications have a extensive future.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of catalyst of photocatalysis Decomposition aquatic products hydrogen, including nano titania cheat array and are grown on the nanometer hole
Molybdenum disulfide array in array, reducing agent carry out reduction removing to the molybdenum disulfide array.
The catalyst of photocatalysis Decomposition aquatic products hydrogen of the present invention, absorbing ability is strong, and light absorption range is wide, photo-generated carrier
Active high, Photocatalyzed Hydrogen Production ability is strong；Nonmetallic plasma resonance light absorption is realized on the basis of the Intrinsic Gettering of material,
The utilization rate of solar energy is greatly improved, excellent performance, the production of unit mass active material are shown in seawater hydrogen manufacturing
Hydrogen amount is up to 2000mmol/h.
After reducing agent carries out reduction removing to the molybdenum disulfide array, the surface phasmon effect of molybdenum disulfide is obvious
Enhancing, and the transformation by 2H phase to 1T phase has occurred in molybdenum disulfide, it is made to show metalline, so that finally obtained different
The hydrogen output of matter structure greatly improves.
Preferably, in the catalyst, the load capacity of molybdenum disulfide is 40.8-61.2 μ g/cm2。
Preferably, the average pore size of nano titania hole array is 40-60nm, with a thickness of 60-80nm.
Preferably, the reducing agent includes one of sodium borohydride, tert-butyl lithium and lithium chloride or a variety of.
The present invention also provides a kind of preparation methods of the catalyst of photocatalysis Decomposition aquatic products hydrogen, including walk as follows
It is rapid:
The growth in situ molybdenum disulfide array in the array of nano titania hole, and reduction removing is carried out to get the light
The catalyst of aquatic products hydrogen is catalytically decomposed.
Preferably, the method for the growth in situ includes: to cheat deposited over arrays metal molybdenum layer in the nano titania,
Vulcanization reaction is carried out under inert gas shielding.
Preferably, the metal molybdenum layer with a thickness of 40-60nm.
Preferably, the method for the vulcanization reaction include: by be deposited with metal molybdenum layer nano titania hole array in
It is placed under heating condition in sour gas atmosphere, carries out vulcanization reaction.It is furthermore preferred that the temperature of the heating is 400-500 DEG C, preferably
It is 450 DEG C.It is further preferred that the sulfur-bearing atmosphere is obtained in a heated condition with the sodium sulfide solution dissolved with sulphur powder
's.
Preferably, the method for the vulcanization reaction includes: to be placed in the nano titania hole battle array for being deposited with metal molybdenum layer
Sodium sulfide solution dissolved with sulphur powder is placed in the upstream warm area of tube furnace by the downstream warm area of tube furnace；Wherein, upstream warm area with
The rate of 4-6 DEG C/min is warming up to 400-500 DEG C, and downstream warm area is warming up to 100-110 DEG C with the rate of 1-3 DEG C/min.It is more excellent
Choosing, the vulcanization reaction insulation reaction 20-30min.
Preferably, the concentration that sulphur powder is dissolved in the sodium sulfide solution is 0.5-1.5mol/L, preferably 1mol/L.More preferably
, the concentration of vulcanized sodium is 0.2-1mol/L, preferably 0.5mol/L in the sodium sulfide solution.
Preferably, the stripping reaction that carries out in reducing agent includes: that will vulcanize resulting to be deposited with the two of molybdenum disulfide
TiOx nano hole array is placed in sodium borohydride solution, carries out hydro-thermal reaction.
Preferably, in the hydro-thermal reaction, temperature is warming up to 140-180 DEG C with the rate of 10-15 DEG C/min.More preferably
, the soaking time of the hydro-thermal reaction is 10-12h.
Preferably, the concentration of the sodium borohydride solution is 0.005-0.021mol/L, preferably 0.01mol/L.
Preferably, the preparation method of nano titania hole array includes: that clean titanium foil is immersed HF/H3PO4In
Carry out anodized.It is furthermore preferred that anodized condition include: respectively using titanium foil and platinum foil as working electrode and
To electrode, the oxidation processes 2-6h under the constant voltage of 8-12V, the oxidation processes 4h preferably under the constant voltage of 10V.
Compared with prior art, the invention has the benefit that
(1) catalyst of photocatalysis Decomposition aquatic products hydrogen of the present invention, absorbing ability is strong, and light absorption range is wide, and photoproduction carries
Stream activity is high, and Photocatalyzed Hydrogen Production ability is strong；
(2) catalyst of photocatalysis Decomposition aquatic products hydrogen of the present invention is realized on the basis of the Intrinsic Gettering of material
Nonmetallic plasma resonance light absorption, is greatly improved the utilization rate of solar energy, shows in seawater hydrogen manufacturing excellent
Performance, the hydrogen output of unit mass active material is up to 2000mmol/h；
(3) preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen of the present invention, simple process and low cost are suitble to
Large-scale production, industrial applications have a extensive future.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the stereoscan photograph that the nano titania that the embodiment of the present invention 1 is prepared cheats array；
Fig. 2 is the scanning electron microscope that the nano titania for being deposited with molybdenum layer that the embodiment of the present invention 1 is prepared cheats array
Photo；
Fig. 3 is that molybdenum disulfide/nano titania hole array catalyst front that the embodiment of the present invention 1 is prepared is swept
Retouch electromicroscopic photograph；
Fig. 4 is that molybdenum disulfide/nano titania after the removing that the embodiment of the present invention 1 is prepared cheats array catalyst
Front scan electromicroscopic photograph；
Fig. 5 is the XRD spectrum of catalyst prepared by the embodiment of the present invention 1；
Fig. 6 is the XRD spectrum of catalyst prepared by the embodiment of the present invention 2；
Fig. 7 is the XRD spectrum of catalyst prepared by comparative example 1；
Fig. 8 is that the hydrogen output of the catalyst of various embodiments of the present invention and comparative example changes over time figure；
Fig. 9 is the sunlight that molybdenum disulfide/nano titania that the embodiment of the present invention 3 is prepared cheats array catalyst
Hydrogen manufacturing yield circulation figure；
Figure 10 is the Raman spectrogram for the catalyst that Example 1 and Example 2 of the present invention is prepared.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
The present invention provides a kind of catalyst of photocatalysis Decomposition aquatic products hydrogen, including nano titania hole array and growth
Molybdenum disulfide array in the nanometer hole array, reducing agent carry out reduction removing to the molybdenum disulfide array.
The catalyst of photocatalysis Decomposition aquatic products hydrogen of the present invention, absorbing ability is strong, and light absorption range is wide, photo-generated carrier
Active high, Photocatalyzed Hydrogen Production ability is strong；Nonmetallic plasma resonance light absorption is realized on the basis of the Intrinsic Gettering of material,
The utilization rate of solar energy is greatly improved, excellent performance, the production of unit mass active material are shown in seawater hydrogen manufacturing
Hydrogen amount is up to 2000mmol/h.
In a preferred embodiment of the invention, in the catalyst, the load capacity of molybdenum disulfide is 40.8-61.2 μ g/
cm2。
In a preferred embodiment of the invention, the average pore size of nano titania hole array is 40-60nm, thick
Degree is 60-80nm.
The present invention also provides a kind of preparation methods of the catalyst of photocatalysis Decomposition aquatic products hydrogen, including walk as follows
It is rapid:
Nano titania hole array in growth in situ molybdenum disulfide array, and carry out reduction removing to get.
In a preferred embodiment of the invention, the method for the growth in situ includes: to cheat in the nano titania
Deposited over arrays metal molybdenum layer, carries out vulcanization reaction under inert gas shielding.
In an of the invention preferred embodiment, the metal molybdenum layer with a thickness of 40-60nm.
In a preferred embodiment of the invention, the method for the vulcanization reaction includes: that will be deposited with the two of metal molybdenum layer
TiOx nano hole array is placed in sour gas atmosphere under heating condition, carries out vulcanization reaction.It is furthermore preferred that the temperature of the heating
Degree is 400-500 DEG C, preferably 450 DEG C.It is further preferred that the sulfur-bearing atmosphere is the sodium sulfide solution to be dissolved with sulphur powder
It obtains in a heated condition.
In a preferred embodiment of the invention, the method for the vulcanization reaction includes: that will be deposited with the two of metal molybdenum layer
TiOx nano hole battle array is placed in the downstream warm area of tube furnace, and the sodium sulfide solution dissolved with sulphur powder is placed in the upstream temperature of tube furnace
Area；Wherein, upstream warm area is warming up to 400-500 DEG C with the rate of 4-6 DEG C/min, and downstream warm area is with the rate liter of 1-3 DEG C/min
Temperature is to 100-110 DEG C.It is furthermore preferred that the vulcanization reaction insulation reaction 20-30min.
In an of the invention preferred embodiment, it is described carried out in reducing agent stripping reaction include: will vulcanize it is resulting
The nano titania hole array for being deposited with molybdenum disulfide is placed in sodium borohydride solution, carries out hydro-thermal reaction.Preferably, described
In hydro-thermal reaction, temperature is warming up to 140-180 DEG C with the rate of 10-15 DEG C/min.It is furthermore preferred that the heat preservation of the hydro-thermal reaction
Time is 10-12h.It is further preferred that the concentration of the sodium borohydride solution is 0.005-0.021mol/L.
In a preferred embodiment of the invention, the concentration that sulphur powder is dissolved in the sodium sulfide solution is 0.5-1.5mol/
L, preferably 1mol/L.It is furthermore preferred that the concentration of vulcanized sodium is 0.2-1mol/L, preferably 0.5mol/L in the sodium sulfide solution.
In a preferred embodiment of the invention, the preparation method of nano titania hole array includes: will be clean
Titanium foil immerse HF/H3PO4Middle carry out anodized.It is furthermore preferred that anodized condition includes: respectively with titanium foil
With platinum foil as working electrode and to electrode, the oxidation processes 2-6h under the constant voltage of 8-12V, preferably in the constant electricity of 10V
Depress oxidation processes 4h.
Embodiment 1
The preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen described in the present embodiment, steps are as follows:
(a) titanium foil with a thickness of 0.05mm is taken, is cleaned by ultrasonic 30min in acetone, ethyl alcohol and deionized water respectively, blows
It is dry, obtain clean titanium foil；
(b) titanium foil clean obtained in step (a) is immersed to HF (solute)/H of 3mol/L3PO4(solvent) electrolyte
In, respectively using titanium foil and platinum foil as working electrode and to electrode, oxidation processes 4h, clear with ethyl alcohol under the constant voltage of 10V
It washes, dries up, obtain the nano titania hole array of honeycomb-patterned ordered arrangement；The scanning electricity of nano titania hole array
Mirror photo is as shown in Figure 1；
(c) deposited over arrays metal molybdenum layer is cheated using electron beam evaporation nano titania obtained in step (b)
40nm obtains the nano titania hole array for being deposited with molybdenum layer；The nano titania hole array for being deposited with molybdenum layer
Stereoscan photograph is as shown in Figure 2；
(d) nano titania that molybdenum layer is deposited with obtained in step (c) hole array is placed in the downstream temperature of tube furnace
Area will be added dropwise in crucible in the sodium sulfide solution of the 0.5mol/L dissolved with 1mol/L sulphur powder, be placed in the upstream temperature of tube furnace
Area；Downstream warm area is first warming up to 450 DEG C with the rate of 5 DEG C/min, then upstream warm area is warming up to the rate of 2 DEG C/min
100 DEG C, insulation reaction 20min, reaction process carries out under an argon atmosphere, obtains molybdenum disulfide/titanium dioxide of high-sequential
The catalyst MoS of nanometer hole array2@TiO2, wherein the load capacity of molybdenum disulfide is 40.8 μ g/cm2；Described two be prepared
Molybdenum sulfide/nano titania hole array catalyst front scan electromicroscopic photograph is as shown in Figure 3.
Embodiment 2
The preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen described in the present embodiment, steps are as follows:
(a) titanium foil with a thickness of 0.05mm is taken, is cleaned by ultrasonic 30min in acetone, ethyl alcohol and deionized water respectively, blows
It is dry, obtain clean titanium foil；
(b) titanium foil clean obtained in step (a) is immersed to HF (solute)/H of 3mol/L3PO4(solvent) electrolyte
In, respectively using titanium foil and platinum foil as working electrode and to electrode, oxidation processes 4h, clear with ethyl alcohol under the constant voltage of 10V
It washes, dries up, obtain the nano titania hole array of honeycomb-patterned ordered arrangement；
(c) deposited over arrays metal molybdenum layer is cheated using electron beam evaporation nano titania obtained in step (b)
40nm obtains the nano titania hole array for being deposited with molybdenum layer；
(d) nano titania that molybdenum layer is deposited with obtained in step (c) hole array is placed in the downstream temperature of tube furnace
Area will be added dropwise in crucible in the sodium sulfide solution of the 0.5mol/L dissolved with 1mol/L sulphur powder, be placed in the upstream temperature of tube furnace
Area；Downstream warm area is first warming up to 450 DEG C with the rate of 5 DEG C/min, then upstream warm area is warming up to the rate of 2 DEG C/min
100 DEG C, insulation reaction 20min, reaction process carries out under an argon atmosphere, obtains molybdenum disulfide/titanium dioxide of high-sequential
The catalyst of nanometer hole array, wherein the load capacity of molybdenum disulfide is 40.8 μ g/cm2；
(e) molybdenum disulfide of high-sequential obtained in step (d)/nano titania hole array catalyst is placed in
In water heating kettle, the sodium borohydride aqueous solution of 0.01mol/L is poured into water heating kettle, water heating kettle is sealed and places it in baking oven；It dries
Box temperature degree is warming up to 160 DEG C, insulation reaction 12h with the rate of 10 DEG C/min, takes out sample after natural cooling, obtains chemistry also
Molybdenum disulfide/nano titania after original removing cheats array catalyst MoS2@TiO2- 160-12h, front scan Electronic Speculum are shone
Piece is as shown in Figure 4.
Embodiment 3
The preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen described in the present embodiment, steps are as follows:
(a) titanium foil with a thickness of 0.05mm is taken, is cleaned by ultrasonic 30min in acetone, ethyl alcohol and deionized water respectively, blows
It is dry, obtain clean titanium foil；
(b) titanium foil clean obtained in step (a) is immersed to HF (solute)/H of 3mol/L3PO4(solvent) electrolyte
In, respectively using titanium foil and platinum foil as working electrode and to electrode, oxidation processes 4h, clear with ethyl alcohol under the constant voltage of 10V
It washes, dries up, obtain the nano titania hole array of honeycomb-patterned ordered arrangement；
(c) deposited over arrays metal molybdenum layer is cheated using electron beam evaporation nano titania obtained in step (b)
60nm obtains the nano titania hole array for being deposited with molybdenum layer；
(d) nano titania that molybdenum layer is deposited with obtained in step (c) hole array is placed in the downstream temperature of tube furnace
Area will be added dropwise in crucible in the sodium sulfide solution of the 0.5mol/L dissolved with 1mol/L sulphur powder, be placed in the upstream temperature of tube furnace
Area；Downstream warm area is first warming up to 450 DEG C with the rate of 5 DEG C/min, then upstream warm area is warming up to the rate of 2 DEG C/min
100 DEG C, insulation reaction 20min, reaction process carries out under an argon atmosphere, obtains molybdenum disulfide/titanium dioxide of high-sequential
The catalyst of nanometer hole array, wherein the load capacity of molybdenum disulfide is 61.2 μ g/cm2；
(e) molybdenum disulfide of high-sequential obtained in step (d)/nano titania hole array catalyst is placed in
In water heating kettle, the sodium borohydride aqueous solution of 0.01mol/L is poured into water heating kettle, water heating kettle is sealed and places it in baking oven；It dries
Box temperature degree is warming up to 160 DEG C, insulation reaction 12h with the rate of 10 DEG C/min, takes out sample after natural cooling, obtains chemistry also
Molybdenum disulfide/nano titania after original removing cheats array catalyst MoS2@TiO2-160-12h。
Embodiment 4
The preparation method of the present embodiment reference implementation example 2, difference are only that: in step (e), sodium borohydride aqueous solution it is dense
Degree is 0.005mol/L.
Embodiment 5
The preparation method of the present embodiment reference implementation example 2, difference are only that: in step (e), sodium borohydride aqueous solution it is dense
Degree is 0.021mol/L.
Embodiment 6
The preparation method of the present embodiment reference implementation example 2, difference are only that: in step (e), oven temperature is with 10 DEG C/min
Rate be warming up to 140 DEG C, obtain electronation removing after molybdenum disulfide/nano titania hole array catalyst MoS2@
TiO2-140-12h。
Embodiment 7
The preparation method of the present embodiment reference implementation example 2, difference are only that: in step (e), oven temperature is with 10 DEG C/min
Rate be warming up to 180 DEG C, obtain electronation removing after molybdenum disulfide/nano titania hole array catalyst MoS2@
TiO2-180-12h。
Comparative example 1
It is used as comparative example 1 using nano titania hole array, the step of preparation method reference implementation example 1 (a) and (b).
Experimental example 1
In order to prove that molybdenum disulfide/nano titania hole has been prepared in the preparation method of embodiment through the invention
Array catalyst, carries out XRD spectrum test by taking Examples 1 and 2, comparative example 1 as an example, and test result as illustrated in figs. 5-7, is distinguished
It is two sulphur after molybdenum disulfide/nano titania hole array of the preparation of embodiment 1, the electronation removing of the preparation of embodiment 2
Change array corresponding XRD spectrum in nano titania hole prepared by molybdenum/nano titania hole array catalyst and comparative example 1.
It can be seen that main diffraction maximum belongs to titanium foil substrate, corresponding PDF card number is 44-1294, and about 14.5 ° can be obvious
See the diffraction maximum of corresponding molybdenum disulfide, wherein the corresponding PDF card number of molybdenum disulfide is: 86-2308.Thus from XRD
Map test result is it is found that molybdenum disulfide/titanium dioxide of photocatalysis Decomposition aquatic products hydrogen has been prepared in the embodiment of the present invention
Nanometer hole array catalyst.
Experimental example 2
The sum of the catalyst for the photocatalysis Decomposition aquatic products hydrogen being prepared for comparative illustration various embodiments of the present invention compares
The performance of the photocatalysis Decomposition aquatic products hydrogen of the catalyst of example 1, the light for the catalyst that each embodiment and comparative example are prepared is urged
The performance for changing decomposition aquatic products hydrogen is tested, and test method is as follows:
The catalyst of each embodiment and comparative example is made to the film of the size of 10mm × 10mm, is placed in the deionization of 15mL
Water and methanol mixing liquid (or 15mL seawater and methanol mixing liquid) in, wherein deionized water and methanol (or seawater
And methanol) volume ratio be 8 ﹕ 2；It uses simulated solar irradiation as visible light source, carries out the experiment that photocatalytic water splitting produces hydrogen, benefit
Gas is acquired with gas chromatograph and calculates yield.The catalyst sample that each embodiment and comparative example are prepared carries out 5 times
Hydrogen test is produced, is averaged, determines hydrogen-producing speed, test result is shown in Table 1；Wherein, A group represent the catalyst for be catalyzed go
The mixing liquid of ionized water and methanol, B group represent the catalyst for being catalyzed the mixing liquid of seawater and methanol.
The photocatalytic water splitting of 1 different catalysts of table produces the rate test result of hydrogen
As can be known from Table 1, the molybdenum disulfide being prepared using various embodiments of the present invention/nano titania hole array is urged
Agent is used for photocatalysis Decomposition aquatic products hydrogen, and hydrogen-producing speed is greatly improved.
In order to further intuitively illustrate the catalysis of catalyst and comparative example 1 that the embodiment of the present invention 1,2,6 and 7 is prepared
The production hydrogen effect of agent is right using deionized water and methanol (volume ratio 8:2) mixing as mixing liquid according to above-mentioned experiment condition
Hydrogen output is tested, and test result is shown in Fig. 8.
As can be known from Fig. 8, the production hydrogen effect for the catalyst that the present invention is removed through electronation is greatly improved.
Experimental example 3
The recycling performance of the catalyst of the photocatalysis Decomposition aquatic products hydrogen in order to further illustrate the present invention, with reality
It for applying the catalyst that example 2 is prepared, is placed in deionized water and the mixing liquid of methanol, wherein deionized water and methanol
Volume ratio is 8 ﹕ 2, uses simulated solar irradiation as visible light source, carries out the circulation experiment that photocatalytic water splitting produces hydrogen, test follows
Hydrogen output under ring use condition, test result are shown in Fig. 9, for sunlight hydrogen manufacturing yield circulation figure.It can be seen that multiple
After recycling, the catalyst still has preferable catalytic performance.
Experimental example 4
In order to further illustrate the present invention after reduction removing, the transformation by 2H phase to 1T phase is had occurred in molybdenum disulfide, into
It has gone following test: Raman spectrum test having been carried out to the catalyst that embodiment 1 and embodiment 2 are prepared, test result is as schemed
Shown in 10, wherein not carrying out only 2H-MoS in the sample of chemical stripping2Raman shift.After chemical stripping, occur
1T-MoS2Raman shift peak, declaratives MoS2Phase transition has occurred.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of catalyst of photocatalysis Decomposition aquatic products hydrogen, which is characterized in that including nano titania hole array and be grown on
Molybdenum disulfide array in the nanometer hole array carries out reduction removing to the molybdenum disulfide array.
2. the catalyst of photocatalysis Decomposition aquatic products hydrogen according to claim 1, which is characterized in that in the catalyst, two
The load capacity of molybdenum sulfide is 40.8-61.2 μ g/cm2。
3. the catalyst of photocatalysis Decomposition aquatic products hydrogen according to claim 1 or 2, which is characterized in that the titanium dioxide
The average pore size of nanometer hole array is 40-60nm, with a thickness of 60-80nm.
4. a kind of preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen, which comprises the steps of:
The growth in situ molybdenum disulfide array in the array of nano titania hole, and reduction removing is carried out to get the photocatalysis
Decompose the catalyst of aquatic products hydrogen.
5. the preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen according to claim 4, which is characterized in that the original
The method of position growth includes: to cheat deposited over arrays metal molybdenum layer in the nano titania, is carried out under inert gas shielding
Vulcanization reaction.
6. the preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen according to claim 5, which is characterized in that the gold
Belong to molybdenum layer with a thickness of 40-60nm.
7. the preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen according to claim 5, which is characterized in that the sulphur
The method for changing reaction includes: that the nano titania hole array for being deposited with metal molybdenum layer is placed in sour gas atmosphere under heating condition
In, carry out vulcanization reaction；
Preferably, the temperature of the heating is 400-500 DEG C；
Preferably, the sulfur-bearing atmosphere is obtained in a heated condition with the sodium sulfide solution dissolved with sulphur powder.
8. the preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen according to claim 5, which is characterized in that the sulphur
The method for changing reaction includes: the downstream warm area that the nano titania hole battle array for being deposited with metal molybdenum layer is placed in tube furnace, will be molten
The upstream warm area that solution has the sodium sulfide solution of sulphur powder to be placed in tube furnace；Wherein, upstream warm area is warming up to the rate of 4-6 DEG C/min
400-500 DEG C, downstream warm area is warming up to 100-110 DEG C with the rate of 1-3 DEG C/min；
Preferably, the vulcanization reaction insulation reaction 20-30min.
9. the preparation method of the catalyst of photocatalysis Decomposition aquatic products hydrogen according to claim 7, which is characterized in that it is described
It includes: that will vulcanize the resulting nano titania hole array for being deposited with molybdenum disulfide to be placed in boron that stripping reaction is carried out in reducing agent
In sodium hydride solution, hydro-thermal reaction is carried out；
Preferably, in the hydro-thermal reaction, temperature is warming up to 140-180 DEG C with the rate of 10-15 DEG C/min；
Preferably, the soaking time of the hydro-thermal reaction is 10-12h.
Preferably, the concentration of the sodium borohydride solution is 0.005-0.021mol/L.
10. according to the preparation method of the catalyst of the described in any item photocatalysis Decomposition aquatic products hydrogen of claim 4-7, feature exists
In the preparation method of nano titania hole array includes: that clean titanium foil is immersed HF/H3PO4Middle carry out anodic oxidation
Processing；
Preferably, anodized condition includes: respectively using titanium foil and platinum foil as working electrode and to electrode, in 8-12V
Constant voltage under oxidation processes 2-6h.
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| CN110170332A (en) * | 2019-06-20 | 2019-08-27 | 中国石油大学(华东) | A kind of carbonitride and preparation method thereof can be used for photocatalysis seawater liberation of hydrogen |
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| JP2015142882A (en) * | 2014-01-31 | 2015-08-06 | 博 久保田 | Hydrogen formation catalyst |
| CN105442012A (en) * | 2016-01-07 | 2016-03-30 | 河南工程学院 | Preparation method and application of composite nanometer material MoS2/TiO2 nanotube array |
| CN106315750A (en) * | 2016-11-01 | 2017-01-11 | 江苏科技大学 | Visible light catalyst molybdenum disulfide loaded titanium dioxide nano-tube electrode as well as preparation method and application thereof |
| CN107723777A (en) * | 2017-10-16 | 2018-02-23 | 南通纺织丝绸产业技术研究院 | The preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot |
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| JP2015142882A (en) * | 2014-01-31 | 2015-08-06 | 博 久保田 | Hydrogen formation catalyst |
| CN105442012A (en) * | 2016-01-07 | 2016-03-30 | 河南工程学院 | Preparation method and application of composite nanometer material MoS2/TiO2 nanotube array |
| CN106315750A (en) * | 2016-11-01 | 2017-01-11 | 江苏科技大学 | Visible light catalyst molybdenum disulfide loaded titanium dioxide nano-tube electrode as well as preparation method and application thereof |
| CN107723777A (en) * | 2017-10-16 | 2018-02-23 | 南通纺织丝绸产业技术研究院 | The preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot |
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