CN106492868B - The method of catalyst and preparation method thereof and photocatalytic hydrogen production by water decomposition - Google Patents
The method of catalyst and preparation method thereof and photocatalytic hydrogen production by water decomposition Download PDFInfo
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- CN106492868B CN106492868B CN201610857666.8A CN201610857666A CN106492868B CN 106492868 B CN106492868 B CN 106492868B CN 201610857666 A CN201610857666 A CN 201610857666A CN 106492868 B CN106492868 B CN 106492868B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- 239000001257 hydrogen Substances 0.000 title claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000004566 IR spectroscopy Methods 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims 1
- 238000001782 photodegradation Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 31
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 239000011521 glass Substances 0.000 description 21
- 239000005297 pyrex Substances 0.000 description 21
- 238000006555 catalytic reaction Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000010835 comparative analysis Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- -1 i.e. Chemical compound 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the methods of fireballing catalyst of a kind of hydrogen manufacturing and preparation method thereof and photocatalytic hydrogen production by water decomposition.The catalyst is in C3N4The compound that Ni-Al-LDH is formed is adulterated, the mass ratio of Ni-Al-LDH and C3N4 is 1:(1.5-19 in the compound).The catalyst the preparation method comprises the following steps: by Ni-Al-LDH and C3N41:(1.5-19 in mass ratio) mixed grinding, until described two materials are in powdered；Solvent is added in mixed-powder after grinding and forms suspension；To suspension centrifugal treating, isolate is obtained；Isolate is dried to obtain catalyst.Using the method for the catalyst hydrogen manufacturing are as follows: will be in reaction solution of the above-mentioned catalyst merging including water and methanol；Wavelength is used to irradiate the reaction solution liquid in the light of 0nm-780nm to generate hydrogen.Catalyst of the invention, the catalyst prepared using method of the invention and photocatalytic hydrogen production by water decomposition method of the invention all have the fireballing advantage of photodegradation water hydrogen manufacturing.
Description
[technical field]
The present invention relates to hydrogen preparation fields more particularly to a kind of fireballing catalyst of photodegradation water hydrogen manufacturing to urge with this is manufactured
The method of agent, and the method using the catalyst hydrogen manufacturing.
[background technique]
With the development in the world, polluted on the earth it is increasingly severe, find out it is a kind of substitute petroleum the energy be badly in need of solve.Hydrogen
Gas is as the most abundant energy of reserves on the earth, and safety efficiently cleans.However hydrogen production is difficult, restrict hydrogen becomes
The development of fungible energy source.Currently, the research in photodegradation water hydrogen manufacturing direction has become a hot topic of research.When photocatalytic hydrogen production by water decomposition
Need to use catalyst, and in the prior art, the rate of catalyst hydrogen manufacturing is lower, is not able to satisfy the needs of hydrogen manufacturing.Develop high property
The photocatalytic hydrogen production by water decomposition of energy is with catalyst then at the key point of photocatalytic hydrogen production by water decomposition.
In recent years, prepare hydrogen based on semiconductor light-catalyst and semiconductor composite and attract wide attention,
Wherein LDH (Layered Double Hydroxide, layered double hydroxide) material as catalysis material or is answered
It closes semiconductor material and has obtained extensive research.LDH is a kind of important anion type laminated clay material, the divalent of laminate and
Trivalent metal cation in laminate high degree of dispersion, and and hydroxyl orderly main structure is formed with covalent bond.Researcher passes through
Reasonable design regulates and controls different types of metal ion, and the hydrotalcite of synthesis imparts the multi-functional characteristic of such material.
Hydrotalcite must be promoted to the application and development of catalysis material applied to photochemical catalyzing field.And current LDH class material
Obtained catalyst in photochemical catalyzing field using unsatisfactory, as number of patent application CN201110376582.X is proposed
A kind of photochemical catalyzing prepares stratiform houghite photocatalyst of hydrogen and preparation method thereof, uses coprecipitation, synthesizes
Serial photodegradation water prepares the stratiform hydrotalcite photochemical catalyst of hydrogen, and hydrogen-producing speed is only 0.314 mmoles of every gram of catalyst
Per hour (0.314mmol/h), producing hydrogen, the effect is unsatisfactory for that.
Therefore, a kind of faster catalyst of hydrogen production rate how is provided, just at a kind of technical issues that need to address！
[summary of the invention]
To overcome LDH class material catalyst in the slow-footed technical problem of photocatalytic hydrogen production by water decomposition, the present invention provides
A kind of fireballing catalyst of photodegradation water hydrogen manufacturing and the method for manufacturing the catalyst, and the method using the catalyst hydrogen manufacturing.
The scheme that the present invention solves technical problem is to provide a kind of preparation method of catalyst, comprising the following steps: by Ni-
Al-LDH and C3N41:(1.5-19 in mass ratio) mixed grinding, until described two materials are in powdered；By the mixing after grinding
Powder is added solvent and forms suspension, needs to be stirred when the mixed-powder forms suspension, stirring rate 1000r/
Min-2000r/min, mixing time are -36h for 24 hours；To suspension centrifugal treating, isolate is obtained；Isolate is dried to obtain
Catalyst is 70 DEG C -90 DEG C to temperature of isolate when dry, and drying time is -36h for 24 hours.
Preferably, catalyst is obtained using freeze-day with constant temperature to isolate.
The scheme that the present invention solves technical problem is to provide a kind of catalyst, is used for photocatalytic hydrogen production by water decomposition gas,
It is prepared using the preparation method of catalyst as described above, is C3N4Adulterate the compound that Ni-Al-LDH is formed.
Preferably, the compound is layer structure, and wherein Ni-Al-LDH is interspersed in C3N4In layer structure.
Preferably, the compound has absorbability to the light of 0nm-780nm.
Preferably, the X-ray diffraction of the compound has C simultaneously3N4(002) feature having in 2 θ=27.47 °
(003) having at 2 θ=11.4 °, 22.4 °, 35.0 ° and 62.0 ° at peak and Ni-Al-LDH, (006), (009) and
(110) characteristic peak.
Preferably, the compound has in infrared spectroscopy in wave number 3150cm-1Transmission peaks.
The present invention also provides a kind of methods of photocatalytic hydrogen production by water decomposition, which comprises the following steps:
It include in the reaction solution of water and methanol by the merging of above-mentioned catalyst；Light using wavelength in 0nm-780nm irradiates institute
Reaction solution is stated to generate hydrogen.
Preferably, when irradiating the reaction solution, while the reaction solution is stirred, and maintain the temperature of reaction solution
20℃-30℃。
Compared with prior art, catalyst composites of the invention are by using special double-metal hydroxide Ni-Al-
LDH and C3N4It is doped according to special ratios, due to maintaining C3N4Layer structure, and Ni-Al-LDH is interspersed in C3N4Stratiform
In structure, catalyst is made to be provided simultaneously with the catalysis characteristics of two kinds of substances, and above-mentioned structure has been multiplied the urging of catalyst
Change function, there is very high hydrogen-producing speed, can reach every gram of catalyst hydrogen output about 200mmol/g per hour, with simple Ni-
Al-LDH and C3N4It compares, hydrogen-producing speed significantly improves.
Compared with prior art, manufacture catalyst of the invention is simple to manufacture, and chemical reaction will not be generated, to environment without dirt
Dye, is only simple physical mixed, also embodies manufacture hydrogen, safeguard the objective of environmental nonpollution.
Compared with prior art, simple using catalyst hydrogen production process of the invention, the rate of hydrogen manufacturing is high, greatly reduces
The cost of hydrogen manufacturing.
The reaction solution is stirred simultaneously when the present invention irradiates the light of the 0nm-780nm, makes catalyst and reaction
Liquid mixing is more uniform, has further speeded up the rate of hydrogen manufacturing.
When the present invention irradiation ultraviolet light and/or visible light simultaneously, 20 DEG C -30 DEG C of temperature in reactor are maintained, protected
Reaction temperature has been demonstrate,proved, has made hydrogen manufacturing speed faster.
[Detailed description of the invention]
Fig. 1 is the XRD (X-ray of the material Ni-Al-LDH (nickel aluminum bimetal hydroxide) of manufacture catalyst of the invention
Diffraction, X-ray diffraction) map.
Fig. 2 is the material C of manufacture catalyst of the invention3N4The XRD spectrum of (carbonitride).
Fig. 3 is Ni-Al-LDH and C of the invention3N4XRD spectrum of the different quality than three kinds of catalyst manufactured after mixing.
Fig. 4 is that the present invention uses SEM (scanning electron microscope scanning electron microscope) to check C3N4
Microscopic appearance result schematic diagram.
Fig. 5 is the schematic diagram for the microscopic appearance result that the present invention checks Ni-Al-LDH using SEM.
Fig. 6 is that the present invention is looked into using TEM (Transmission Electron Microscope transmission electron microscope)
See the schematic diagram of the microscopic appearance result of catalyst.
Fig. 7 is C of the invention3N4Light absorpting ability measurement result schematic diagram.
Fig. 8 is the schematic diagram of the measurement result of the light absorpting ability of Ni-Al-LDH of the invention.
Fig. 9 is Ni-Al-LDH and C of the present invention3N4The measurement result of light absorpting ability of the catalyst that is compounded to form show
It is intended to.
Figure 10 is catalyst of the invention, C3N4With the comparison diagram of the examination of infrared spectrum result of Ni-Al-LDH.
Figure 11 is the partial enlargement diagram of Figure 10.
Figure 12 is the flow diagram for the method that the present invention prepares catalyst.
Figure 13 is flow diagram of the present invention using the method for catalyst preparation hydrogen.
[specific embodiment]
In order to make the purpose of the present invention, technical solution and advantage are more clearly understood, below in conjunction with attached drawing and embodiment,
The present invention will be described in further detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention,
It is not intended to limit the present invention.
Catalyst of the invention is in C3N4The compound that Ni-Al-LDH is formed is adulterated, Ni-Al-LDH/ is denoted as
C3N4.Ni-Al-LDH and C in compound3N4Mass ratio be preferably 1:(1.5-19).Adulterate the mutual complex of latter two material
At compound, but still keep layer structure characteristic, wherein Ni-Al-LDH is interspersed in C3N4In layer structure, to 0nm-
The light (ultraviolet light and visible light) of 780nm has absorbability, and absorbability is very high, keeps the efficiency of photodegradation water hydrogen manufacturing significant
It improves.
Above-mentioned Ni-Al-LDH and C3N4Mass ratio be 1:9 when, by compound be labeled as 10-LDH/90-C3N4, above-mentioned
Ni-Al-LDH and C3N4Mass ratio when being 1:4 (i.e. 2:8), the compound made according to the method described above is labeled as 20-
LDH/80-C3N4, above-mentioned Ni-Al-LDH and C3N4Mass ratio when being about 1:2.3 (i.e. 3:7), produce according to the method described above
The compound come is labeled as 30-LDH/70-C3N4。
Referring to Fig. 1, Fig. 2 and Fig. 3, Fig. 1 are the XRD characterizations to Ni-Al-LDH, Fig. 2 is to C3N4XRD characterization, Fig. 3
It is to 10-LDH/90-C3N4, 20-LDH/80-C3N4And 30-LDH/70-C3N4The XRD characterization of three kinds of compounds.To above-mentioned three kinds
The XRD characterization of compound can be seen that single-phase Ni-Al-LDH respectively in 2 θ=11.4 °, and 22.4 °, 35.0 °, 39.7 °,
46.5 °, the characteristic diffraction peak (003) of 62.0 ° of Ni-Al-LDHss for occurring corresponding with 72.8 °, (006), (009), (015),
(018), (110) and (116).Single-phase C3N4It is respectively corresponded 2 θ=13.04 ° and 27.47 ° and C has occurred3N4(100) and
(002) characteristic diffraction peak, three kinds of complex catalysts all have C3N4(002) characteristic peak, while having corresponding to Ni-Al-
(003) of LDH, (006), (009) and (110) characteristic peak, and with the increase of Ni-Al-LDH content in appropriate range,
It is increased with it corresponding to the intensity of the characteristic peak of Ni-Al-LDH, illustrates that there are C in above-mentioned complex catalyst3N4And Ni-Al-
Chemical change does not occur for LDH, this two kinds of materials, also holding the starting substance.
Referring to Figure 4 together and Fig. 5, Fig. 4 C3N4Microscopic appearance characterized using SEM, Fig. 5 is Ni-Al-LDH's
Microscopic appearance is characterized using SEM.It can be seen that C3N4Particle is layer structure made of being accumulated as laminated structure, i.e. C3N4
It is to be stacked by laminated structure that a large amount of partial sizes are 200nm or so is unordered, and laminated structure is equally to have in large quantities more
Small laminated structure stacks.Ni-Al-LDH is also layer structure made of being stacked as laminated structure, and the heap of laminated structure
It is folded then follow certain rule, it is that the laminated structure for being about 100nm by thickness piles up shape together with essentially identical quantity
The stratiform monomer cluster structure for being about 400nm at partial size.By analysis it is found that C known to analysis3N4It is by different with Ni-Al-LDH
Layer structure composition.From design feature, since both materials are both with lamellar character, during doping also more
Contacting with each other and uniformly mixing conducive to two kinds of materials.
Referring to Fig. 6, Fig. 6 is C3N4Adulterate the compound 20-LDH/80-C of Ni-Al-LDH3N4Microscopic appearance use
TEM is characterized, it can be seen that complex catalyst has layer structure under microcosmic, which is amorphous.To the area
The result that domain carries out electronic diffraction can see diffraction pattern without clearly diffraction ring, hence it is demonstrated that the region is unbodied
C3N4.In addition to unbodied C3N4, part high power transmission region has apparent lattice, and corresponding at this is Ni-Al-LDH.It is logical
It crosses TEM and demonstrates C3N4It is mutually compound with Ni-Al-LDH, while also further demonstrating the composite material and still keeping stratiform knot
The characteristic of structure, Ni-Al-LDH is substantially uniform to be interspersed in C3N4Layer structure in.
Referring to Fig. 7, Fig. 8 and Fig. 9, respectively shows single-phase Ni-Al-LDH and single-phase C3N4And the two is compound
The complex catalyst 10-LDH/90-C of formation3N4The measurement of light absorpting ability is carried out.The result shows that C3N4Not only to ultraviolet
Light (0nm < wavelength < 400nm) has very strong absorbability, and also has to visible light (400nm < wavelength < 780nm) stronger
Absorbability.And Ni-Al-LDH only has certain absorbability to ultraviolet light, and absorption region is very narrow, only wavelength <
The region of 250nm has stronger absorbability.And compound 10-LDH/90-C3N4Two kinds of single-phase materials are then effectively drawn
Effective absorption bands, not only increase the absorbability in UV light region, while extending the absorption in visible light wave range
Ability, i.e., it has absorbability to the light (ultraviolet light and visible light) of 0nm-780nm, and absorbability is very high, compound 10-
LDH/90-C3N4It is two kinds of materials at two to three times of the sum of ultraviolet light wave band absorbability in the absorbability of ultraviolet light wave band,
It is two kinds of materials at four to five times of the sum of visible light wave range absorbability in the absorbability of visible light wave range, therefore is using
When complex catalyst hydrogen manufacturing of the invention, preferably irradiating ultraviolet light and/or visible light.It is further from the angle of light absorpting ability
Explain compound 10-LDH/90-C3N4Activity during photocatalytic cleavage aquatic products hydrogen is higher than single-phase Ni-Al-LDH
And C3N4Activity.Ni-Al-LDH and C3N4Composite strengthening C3N4The electric conductivity of itself improves photoexcitation carrier
Delivery rate, increase electron-hole separative efficiency, fundamentally enhance C3N4Photocatalytic activity.
Figure 10 and Figure 11 are please referred to, Figure 10 and Figure 11 are illustrated to three kinds of complex catalyst 10-LDH/90-C3N4, 20-
LDH/80-C3N4, 30-LDH/70-C3N4With single-phase C3N4And the examination of infrared spectrum of single-phase Ni-Al-LDH.From figure
It can be seen that Ni-Al-LDH has the typical transmission peaks of layered double hydroxide class material, wherein wave number 3353cm-1With
1639cm-1Transmission peaks corresponded to the bending vibration of O-H in layered double hydroxide material, and wave number 1349cm-1It is then right
It should be vibrated in the anion in layered double hydroxide intercalation.For single-phase C3N4, in wave number 3150cm-1Transmission
Peak also corresponds to the bending vibration of O-H, these O-H are from C3N4The hydrone of absorption.Using the preparation method system of above-mentioned doping
The transmission peaks of the standby three kinds of complex catalysts come out and single-phase C3N4It is substantially completely overlapped, compound also has in infrared spectroscopy
Have in wave number 3150cm-1Transmission peaks, it is lower that this is attributed to the content of Ni-Al-LDH in the composite, while also demonstrating
During entire doping, C3N4Its basic structure is maintained well.Although on the other hand also illustrating that the compound after doping is urged
The performance of agent, which has, to be obviously improved, however C3N4Structure substantially there is no variation, Ni-Al-LDH as doping partly leads
Body material has and material of main part C3N4Similar layer structure, this reduces bulk catalyst C to a certain extent3N4And visitor
Estrangement between body doped catalyst Ni-Al-LDH, Ni-Al-LDH and C3N4Between mix more thoroughly.
Figure 12 is please referred to, the present invention also provides a kind of method for preparing the catalyst, the preparation methods of the catalyst
The following steps are included:
Step S1: by Ni-Al-LDH and C3N41:(1.5-19 in mass ratio) mixed grinding, until described two materials are in
It is powdered；
Step S2: solvent is added in the mixed-powder after grinding and forms suspension；
Step S3: to suspension centrifugal treating, isolate is obtained；
Step S4: isolate is dried to obtain catalyst.
When carrying out step S1, the Ni-Al-LDH and C of use3N4Mass ratio be preferably 1:(2.3-9), more preferably 1:4.
When carrying out step S2, need to be stirred when mixed-powder forms suspension, stirring rate when stirring is preferable
For 800r/min or more, preferably 800r/min-2000r/min, further preferably 1000r/min-2000r/min, stirring
Time is preferably 18h or more, preferably 18h-36h, further preferably for 24 hours -36h, and when stirring preferably uses blender,
Preferably magnetic stirring apparatus can make to stir more uniform.Solvent and Ni-Al-LDH and C used3N4It is immiscible, preferred solvents
Using deionized water, mountain spring water, mineral water, other water such as tap water, preferably deionized water.
When carrying out step S4, freeze-day with constant temperature is preferably carried out when dry, dry temperature is preferably 60 DEG C -100 DEG C, more preferably
It is 70 DEG C -90 DEG C, preferably 80 DEG C, the dry time is preferably 18h or more, preferably 18h-36h, further preferably
24h-36h。
The catalyst as made from this method has the advantages that Photocatalyzed Hydrogen Production gas is high-efficient.
Figure 13 is please referred to, the present invention also provides a kind of method using the catalyst preparation hydrogen, specific preparation process
The following steps are included:
Step T1: including in the reaction solution of water and methanol by above-mentioned catalyst merging；
Step T2: wavelength is used to irradiate the reaction solution in the light of 0nm-780nm to generate hydrogen.
In the step T1, the volume ratio of water and methanol in the reaction solution is preferably (1.5-9): 1, more preferably
For (3-5): 1, preferably 4:1, the water are deionized water, mountain spring water, other any kind of water such as tap water, mineral water,
Preferably deionized water.It is appreciated that the amount of above-mentioned catalyst can be added according to conventional ratio in reaction solution namely catalyst
Amount ratio with reaction solution is preferably 1g:(500-6000) ml, preferably 1g:(1000-3000) ml, further preferably
1g:2000ml。
In the step T2, when being irradiated to the reaction solution, preferably, maintaining 20 DEG C -30 of temperature in reactor
DEG C, more preferably temperature be 23 DEG C, 24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, preferably 25 DEG C.The light of irradiation 0nm-780nm preferably uses
Xe-Hg lamp.Preferably, when being irradiated to the reaction solution, while the reaction solution is stirred, stirring rate is preferably
200r/min-500r/min, more preferably 250r/min-400r/min, preferably 300r/min.It, can be with as a kind of deformation
First start to stir, then irradiates the light of 0nm-780nm.It is deformed as another kind, can first irradiate the light of 0nm-780nm, then carry out
Stirring.
As a kind of selection, in step T1, the reaction solution of the addition catalyst is placed in container, and to the appearance
Device repeatedly vacuumize and is operated with filling with inert gas, then carries out step T2.The reactor is preferably closed container, excellent
It is selected as Pyrex glass reactor.This step is carried out, the incoherent gas for not having to influence measurement hydrogen in reactor can be made,
It can be measured in detail to the hydrogen output of catalyst hydrogen manufacturing.
In order to which the catalyst is further detailed, the specific experiment group and contrast groups being listed below.
Experimental group 1:
Make catalyst:
The C of the Ni-Al-LDH and 2g of 0.5g are weighed respectively3N4, i.e. Ni-Al-LDH and C3N4Mass ratio be 1:4, and
Mixed grinding in corundum mortar, until described two materials are in powdered；
Powdered product is placed in a beaker, the deionized water for adding 50ml forms suspension, and uses magnetic stirring apparatus
It is stirred, mixing speed 1000r/min, mixing time is for 24 hours；
The suspension after stirring is handled with centrifuge, obtains isolate；
By isolate, for 24 hours, obtained article is catalyst for drying in 80 DEG C of thermostatic drying chambers.
Verify catalytic activity (using catalyst preparation hydrogen):
The catalyst 50mg that precise is made, is then dissolved in 100ml reaction solution, and reaction solution is set
Enter Pyrex glass reactor, the reaction solution is made of 80ml deionized water and 20ml methanol, i.e. deionized water and methanol
Volume ratio is 4:1；
To Pyrex glass reactor carry out it is repeated multiple times vacuumize and applying argon gas operation, until reaction system in do not have
Air；
Pyrex glass temperature of reactor is maintained 25 DEG C always, and to the reaction solution added with catalyst keep with
The revolving speed holding of 300r/min continuously stirs, and the Xe-Hg lamp of power position 880w is used using visible-ultraviolet irradiation light source
(Newport, RI) is filtered the infrared light in incident light source from the incidence of reactor top, and using Circulated water filter, with
Ensure that incident light is ultraviolet light and visible light；
And since photochemical catalyzing reaction after, form and aspect map is automatically anti-to Pyrex glass by chronomere of 1h
It answers gas in device to be sampled, analyze hydrogen content therein and keeps a record.
With 20h for an evaluation cycle, light source is closed when reaction carries out 20h, stops reaction, it is anti-to Pyrex glass
Device is answered to be vacuumized for several times and filling with inert gas, until not having a upper evaluation cycle to remain in Pyrex glass reactor
Hydrogen.When judging whether there is hydrogen, the gas in Pyrex glass reactor is examined preferably by form and aspect map
It surveys.
Then light source is opened, the evaluation cycle of new 20h is started, carries out four evaluation cycles altogether.
Experimental group 2:
When making catalyst, the C of the Ni-Al-LDH and 2.25g of 0.25g are weighed respectively3N4, i.e. Ni-Al-LDH and C3N4Matter
Amount is ground in corundum mortar than being 1:9, until described two materials are in powdered；The experiment of other conditions and experimental group 1
Condition is identical.
Experimental group 3:
When making catalyst, the C of the Ni-Al-LDH and 1.75g of 0.75g are weighed respectively3N4, i.e. Ni-Al-LDH and C3N4's
Mass ratio is 1:2.3, and is ground in corundum mortar, until described two materials are in powdered；Other conditions and experimental group 1
Experiment condition is identical.
Experimental group 4:
When making catalyst, the C of the Ni-Al-LDH and 2.375g of 0.125g are weighed respectively3N4, i.e. Ni-Al-LDH and C3N4
Mass ratio be 1:19, and ground in corundum mortar, until described two materials are in powdered；Other conditions and experimental group 1
Experiment condition it is identical.
Experimental group 5:
When making catalyst, the C of the Ni-Al-LDH and 1.5g of 1g are weighed respectively3N4, i.e. Ni-Al-LDH and C3N4Quality
It than for 1:1.5, and is ground in corundum mortar, until described two materials are in powdered；The experiment of other conditions and experimental group 1
Condition is identical.
Experimental group 6:
When making catalyst, powdered product is placed in a beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed 800r/min, mixing time is for 24 hours；The experiment of other conditions and experimental group 1
Condition is identical.
Experimental group 7:
When making catalyst, powdered product is placed in a beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed 1000r/min, mixing time 18h；The reality of other conditions and experimental group 1
It is identical to test condition.
Experimental group 8:
When making catalyst, by isolate, for 24 hours, obtained article is catalyst for drying in 60 DEG C of thermostatic drying chambers；
Other conditions are identical as the experiment condition of experimental group 1.
Experimental group 9:
When making catalyst, by isolate, for 24 hours, obtained article is catalyst for drying in 100 DEG C of thermostatic drying chambers；
Other conditions are identical as the experiment condition of experimental group 1.
Experimental group 10:
When making catalyst, isolate is dried into 18h in 800 DEG C of thermostatic drying chambers, obtained article is catalyst；
Other conditions are identical as the experiment condition of experimental group 1.
Experimental group 11:
When verifying catalytic activity, then the catalyst 50mg that precise is made is dissolved in 100ml reaction solution
In, and reaction solution is placed in Pyrex glass reactor, the reaction solution is made of 60ml deionized water and 40ml methanol, i.e.,
Deionized water and methanol volume ratio are 1.5:1；Other conditions are identical as the experiment condition of experimental group 1.
Experimental group 12:
When verifying catalytic activity, then the catalyst 50mg that precise is made is dissolved in 100ml reaction solution
In, and reaction solution is placed in Pyrex glass reactor, the reaction solution is made of 90ml deionized water and 10ml methanol, i.e.,
Deionized water and methanol volume ratio are 9:1；Other conditions are identical as the experiment condition of experimental group 1.
Experimental group 13:
When verifying catalyst activity, Pyrex glass temperature of reactor is maintained 25 DEG C always, and to added with catalysis
The reaction solution of agent keeps continuously stirring with the revolving speed holding of 200r/min, and uses power position using visible-ultraviolet irradiation light source
The Xe-Hg lamp (Newport, RI) of 880w utilizes Circulated water filter will be in incident light source from the incidence of reactor top
Infrared light filtering, to ensure incident light as ultraviolet light and visible light；Other conditions are identical as the experiment condition of experimental group 1.
Experimental group 14:
When verifying catalyst activity, Pyrex glass temperature of reactor is maintained 25 DEG C always, and to added with catalysis
The reaction solution of agent keeps continuously stirring with the revolving speed holding of 500r/min, and uses power position using visible-ultraviolet irradiation light source
The Xe-Hg lamp (Newport, RI) of 880w utilizes Circulated water filter will be in incident light source from the incidence of reactor top
Infrared light filtering, to ensure incident light as ultraviolet light and visible light；Other conditions are identical as the experiment condition of experimental group 1.
Experimental group 15:
When verifying catalyst activity, Pyrex glass temperature of reactor is maintained 20 DEG C always, and to added with catalysis
The reaction solution of agent keeps continuously stirring with the revolving speed holding of 300r/min, and uses power position using visible-ultraviolet irradiation light source
The Xe-Hg lamp (Newport, RI) of 880w utilizes Circulated water filter will be in incident light source from the incidence of reactor top
Infrared light filtering, to ensure incident light as ultraviolet light and visible light；Other conditions are identical as the experiment condition of experimental group 1.
Experimental group 16:
When verifying catalyst activity, Pyrex glass temperature of reactor is maintained 30 DEG C always, and to added with catalysis
The reaction solution of agent keeps continuously stirring with the revolving speed holding of 300r/min, and uses power position using visible-ultraviolet irradiation light source
The Xe-Hg lamp (Newport, RI) of 880w utilizes Circulated water filter will be in incident light source from the incidence of reactor top
Infrared light filtering, to ensure incident light as ultraviolet light and visible light；Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 1:
Directly come using Ni-Al-LDH as catalyst applications using other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 2:
Directly with C3N4Come as catalyst applications using other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 3:
When making catalyst, the C of the Ni-Al-LDH and 2.4g of 0.1g are weighed respectively3N4, Ni-Al-LDH and C3N4By matter
Amount is mixed than the ratio for being 1:24, and is ground in corundum mortar, until described two materials are in powdered；Other conditions and reality
The experiment condition for testing group 1 is identical.
Contrast groups 4:
When making catalyst, the C of the Ni-Al-LDH and 1.25g of 1.25g are weighed respectively3N4, Ni-Al-LDH and C3N4It presses
The ratio that mass ratio is 1:1 mixes, and grinds in corundum mortar, until described two materials are in powdered；Other conditions with
The experiment condition of experimental group 1 is identical.
Contrast groups 5:
When making catalyst, powdered product is placed in a beaker, the deionized water of 50ml is added, and uses magnetic agitation
Device is stirred, mixing speed 600r/min, and mixing time is for 24 hours；Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 6:
When making catalyst, powdered product is placed in a beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed 1500r/min, mixing time is for 24 hours；The reality of other conditions and experimental group 1
It is identical to test condition.
Contrast groups 7:
When making catalyst, powdered product is placed in a beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed 1000r/min, mixing time 15h；The reality of other conditions and experimental group 1
It is identical to test condition.
Contrast groups 8:
When making catalyst, powdered product is placed in a beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed 1000r/min, mixing time 30h；The reality of other conditions and experimental group 1
It is identical to test condition.
Contrast groups 9:
When making catalyst, by isolate, for 24 hours, obtained article is catalyst for drying in 50 DEG C of thermostatic drying chambers；
Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 10:
When making catalyst, by isolate, for 24 hours, obtained article is catalyst for drying in 110 DEG C of thermostatic drying chambers；
Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 11:
When making catalyst, isolate is dried into 15h in 80 DEG C of thermostatic drying chambers, obtained article is catalyst；
Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 12:
When making catalyst, isolate is dried into 30h in 80 DEG C of thermostatic drying chambers, obtained article is catalyst；
Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 13:
When verifying catalytic activity, then the catalyst 50mg that precise is made is dissolved in 100ml reaction solution
In, and reaction solution is placed in Pyrex glass reactor, the reaction solution is made of 50ml deionized water and 50ml methanol, i.e.,
Deionized water and methanol volume ratio are 1:1；Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 14:
When verifying catalytic activity, then the catalyst 50mg that precise is made is dissolved in 100ml reaction solution
In, and reaction solution is placed in Pyrex glass reactor, the reaction solution is made of 95ml deionized water and 5ml methanol, i.e.,
Deionized water and methanol volume ratio are 19:1；Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 15:
When verifying catalyst activity, Pyrex glass temperature of reactor is maintained 25 DEG C always, and to added with catalysis
The reaction solution of agent keeps continuously stirring with the revolving speed holding of 100r/min, and uses power position using visible-ultraviolet irradiation light source
The Xe-Hg lamp (Newport, RI) of 880w utilizes Circulated water filter will be in incident light source from the incidence of reactor top
Infrared light filtering, to ensure incident light as ultraviolet light and visible light；Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 16:
When verifying catalyst activity, Pyrex glass temperature of reactor is maintained 25 DEG C always, and to added with catalysis
The reaction solution of agent keeps continuously stirring with the revolving speed holding of 700r/min, and uses power position using visible-ultraviolet irradiation light source
The Xe-Hg lamp (Newport, RI) of 880w utilizes Circulated water filter will be in incident light source from the incidence of reactor top
Infrared light filtering, to ensure incident light as ultraviolet light and visible light；Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 17:
When verifying catalyst activity, Pyrex glass temperature of reactor is maintained 10 DEG C always, and to added with catalysis
The reaction solution of agent keeps continuously stirring with the revolving speed holding of 300r/min, and uses power position using visible-ultraviolet irradiation light source
The Xe-Hg lamp (Newport, RI) of 880w utilizes Circulated water filter will be in incident light source from the incidence of reactor top
Infrared light filtering, to ensure incident light as ultraviolet light and visible light；Other conditions are identical as the experiment condition of experimental group 1.
Contrast groups 18:
When verifying catalyst activity, Pyrex glass temperature of reactor is maintained 40 DEG C always, and to added with catalysis
The reaction solution of agent keeps continuously stirring with the revolving speed holding of 300r/min, and uses power position using visible-ultraviolet irradiation light source
The Xe-Hg lamp (Newport, RI) of 880w utilizes Circulated water filter will be in incident light source from the incidence of reactor top
Infrared light filtering, to ensure incident light as ultraviolet light and visible light；Other conditions are identical as the experiment condition of experimental group 1.
Experimental result: as shown in Table 1 and Table 2.
Different condition comparative situation table when table 1 makes catalyst
Note: in table 1, Ni-Al-LDH and C3N4Ratio is mass ratio, and the unit of mixing speed is rpm (r/min), is stirred
The unit for mixing the time is hour (h), and the unit of drying temperature is degree Celsius (DEG C), and the unit of drying time is hour (h).
Different condition comparative situation table when table 2 verifies catalyst activity
Note: in table 2, the unit of mixing speed is rpm (r/min), reaction temperature refers to that Pyrex glass reacts
The temperature that device temperature maintains always, the unit of reaction temperature are degree Celsius (DEG C), and the unit of hydrogen output is mM/every gram of catalysis
Agent (mmol/gcat)。
From the experiment knot of experimental group 1, experimental group 2, experimental group 3, experimental group 4, experimental group 5, contrast groups 1 and contrast groups 2
Fruit comparative analysis is it is found that in the component of catalyst of the invention, Ni-Al-LDH and C3N4Mass ratio be preferably 0.5:9.5-
4:6, more preferably 1:9 or 2:8 or 3:7, preferably 2:8.
From the experimental result comparative analysis of experimental group 1, experimental group 6, contrast groups 5 and contrast groups 6 it is found that preparation of the invention
The agitation phases of catalyst, when mixing speed is more than 1000r/min, mixing speed, which becomes larger, has not significant impact hydrogen output,
Therefore mixing speed is preferably 800r/min or more, more preferably 800r/min-2000r/min, preferably 1000r/min-
2000r/min。
From the experimental result comparative analysis of experimental group 1, experimental group 7, contrast groups 7 and contrast groups 8 it is found that preparation of the invention
The agitation phases of catalyst, upon agitation between be more than for 24 hours, mixing time is elongated to have not significant impact hydrogen output, thus stir when
Between be preferably 18h or more, more preferably 18h-36h, preferably for 24 hours -36h.
From the experimental result comparative analysis of experimental group 1, experimental group 8, experimental group 9, contrast groups 9 and contrast groups 10 it is found that
The centrifugal drying stage for preparing catalyst of the invention, drying temperature are preferably 60 DEG C -100 DEG C, and more preferably 70 DEG C -90
DEG C, preferably 80 DEG C.
From the experimental result comparative analyses of experimental group 1, experimental group 10, contrast groups 11 and contrast groups 12 it is found that the present invention
The centrifugal drying stage for preparing catalyst, when drying between be more than for 24 hours that drying time is elongated not to have obvious shadow to hydrogen output
It rings, therefore drying time is preferably 18h or more, more preferably 18h-36h, preferably for 24 hours -36h.
From test group 1, contrast groups 1, contrast groups 2 are as can be seen that Ni-Al-LDH and C3N4The catalyst that is mixed produce
Hydrogen rate are as follows: every gram of catalyst hydrogen output is about 200mmol/h, and every gram of catalyst hydrogen output of simple Ni-Al-LDH is about
9mmol/h, simple C3N4Every gram of catalyst hydrogen output is about 39mmol/h.Therefore Ni-Al-LDH and C3N4It is made after physical mixed
Catalyst hydrogen output and hydrogen-producing speed greatly improve.
From test group 1, experimental group 11, experimental group 12, contrast groups 13 and contrast groups 14 are as can be seen that of the invention uses catalysis
When agent prepares hydrogen, the ratio of water and methanol in reaction solution used is preferably (1.5-9): 1, preferably (3-5): 1, into
One step is preferably 4:1.
From test group 1, experimental group 13, experimental group 14, contrast groups 15 and contrast groups 16 are as can be seen that of the invention uses catalysis
When agent prepares hydrogen, when to reaction solution irradiating ultraviolet light and/or visible light in the reactor, while to the reaction solution into
Row stirring, stirring rate is preferably 200r/min-500r/min, more preferably 250r/min-400r/min, preferably
300r/min。
From test group 1, experimental group 15, experimental group 16, contrast groups 17 and contrast groups 18 are as can be seen that of the invention uses catalysis
When agent prepares hydrogen, when to reaction solution irradiating ultraviolet light and/or visible light in the reactor, the temperature in reactor is maintained
Preferably 20 DEG C -30 DEG C, more preferably 23 DEG C -27 DEG C, preferably 25 DEG C.
Compared with prior art, catalyst composites of the invention are by using special double-metal hydroxide Ni-Al-
LDH and C3N4It is doped according to special ratios, due to maintaining C3N4Layer structure, and Ni-Al-LDH is interspersed in C3N4Stratiform
In structure, catalyst is made to be provided simultaneously with the catalysis characteristics of two kinds of substances, and above-mentioned structure has been multiplied the urging of catalyst
Change function, there is very high hydrogen-producing speed, can reach every gram of catalyst hydrogen output about 200mmol/g per hour, with simple Ni-
Al-LDH and C3N4It compares, hydrogen-producing speed significantly improves.
Compared with prior art, manufacture catalyst of the invention is simple to manufacture, and chemical reaction will not be generated, to environment without dirt
Dye, is only simple physical mixed, also embodies manufacture hydrogen, safeguard the objective of environmental nonpollution.
Compared with prior art, simple using catalyst hydrogen production process of the invention, the rate of hydrogen manufacturing is high, greatly reduces
The cost of hydrogen manufacturing.
The reaction solution is stirred simultaneously when the present invention irradiates the ultraviolet light and/or visible light, make catalyst and
Reaction solution mixing is more uniform, has further speeded up the rate of hydrogen manufacturing.
When the present invention irradiation ultraviolet light and/or visible light simultaneously, 20 DEG C -30 DEG C of temperature in reactor are maintained, protected
Reaction temperature has been demonstrate,proved, has made hydrogen manufacturing speed faster.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in original of the invention
Made any modification within then, equivalent replacement and improvement etc. should all be comprising within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of catalyst, which comprises the following steps:
By Ni-Al-LDH and C3N41:(1.5-19 in mass ratio) mixed grinding, until described two materials are in powdered；It will grind
Mixed-powder after mill is added solvent and forms suspension, needs to be stirred when the mixed-powder forms suspension, stirring speed
Rate is 1000r/min-2000r/min, and mixing time is -36h for 24 hours；To suspension centrifugal treating, isolate is obtained；It will separation
Object is dried to obtain catalyst, is 70 DEG C -90 DEG C to temperature of isolate when dry, drying time is -36h for 24 hours.
2. the preparation method of catalyst as described in the appended claim 1, it is characterised in that: urged using freeze-day with constant temperature isolate
Agent.
3. a kind of catalyst is used for photocatalytic hydrogen production by water decomposition gas, it is characterised in that: it is using as described in the appended claim 1
The preparation method of catalyst prepare, which is in C3N4Adulterate the compound that Ni-Al-LDH is formed.
4. catalyst as claimed in claim 3, it is characterised in that: the compound is layer structure, and wherein Ni-Al-LDH is worn
It is inserted in C3N4In layer structure.
5. catalyst as claimed in claim 3, it is characterised in that: the compound, which has the light of 0nm-780nm, absorbs energy
Power.
6. catalyst as claimed in claim 3, it is characterised in that: the X-ray diffraction of the compound has C simultaneously3N4?
(002) characteristic peak that 2 θ=27.47 ° have and Ni-Al-LDH's has at 2 θ=11.4 °, 22.4 °, 35.0 ° and 62.0 °
(003) having, (006), (009) and (110) characteristic peak.
7. catalyst as claimed in claim 3, it is characterised in that: the compound has in infrared spectroscopy in wave number 3150cm-1Transmission peaks.
8. a kind of method of photocatalytic hydrogen production by water decomposition, which comprises the following steps:
It include in the reaction solution of water and methanol by catalyst as claimed in claim 3 merging；Using wavelength 0nm-780nm light
The reaction solution is irradiated to generate hydrogen.
9. the method for photocatalytic hydrogen production by water decomposition as claimed in claim 8, it is characterised in that: when irradiating the reaction solution,
The reaction solution is stirred simultaneously, and maintains 20 DEG C -30 DEG C of temperature of reaction solution.
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