CN106492868A - Catalyst and preparation method thereof and the method for photocatalytic hydrogen production by water decomposition - Google Patents
Catalyst and preparation method thereof and the method for photocatalytic hydrogen production by water decomposition Download PDFInfo
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- CN106492868A CN106492868A CN201610857666.8A CN201610857666A CN106492868A CN 106492868 A CN106492868 A CN 106492868A CN 201610857666 A CN201610857666 A CN 201610857666A CN 106492868 A CN106492868 A CN 106492868A
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- ldh
- reactant liquor
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- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 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 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 14
- 239000000376 reactant Substances 0.000 claims abstract description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 18
- 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 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 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
- 238000006555 catalytic reaction Methods 0.000 description 21
- 239000011521 glass Substances 0.000 description 21
- 239000005297 pyrex Substances 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 150000002431 hydrogen Chemical class 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
- 238000010586 diagram Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000010835 comparative analysis Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- -1 i.e. Chemical compound 0.000 description 4
- 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
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 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
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect 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
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 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
- 239000003208 petroleum Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
- B01J27/24—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
A kind of the present invention relates to fireballing catalyst of hydrogen manufacturing and preparation method thereof, and the method for photocatalytic hydrogen production by water decomposition.The catalyst is in C3N4The compound that doping Ni Al LDH are formed, in the compound, the mass ratio of Ni Al LDH and C3N4 is 1：(1.5‑19).The preparation method of the catalyst is：By Ni Al LDH and C3N4In mass ratio 1：(1.5 19) mixed grinding, until described two materials are in powder；Mixed-powder after by grinding adds solvent to form suspension；To suspension centrifugal treating, separator is obtained；Separator is dried to obtain catalyst.Adopt the method for the catalyst hydrogen manufacturing for：Above-mentioned catalyst is inserted in the reactant liquor including water and methyl alcohol；Adopt reactant liquor liquid described in light irradiation of the wavelength in 0nm 780nm to produce hydrogen.The catalyst of the present invention, the catalyst prepared using the method for the present invention, and the photocatalytic hydrogen production by water decomposition method of the present invention all possesses the fireballing advantage of light hydrogen production by water decomposition.
Description
【Technical field】
The present invention relates to hydrogen preparation field, more particularly to a kind of fireballing catalyst of smooth hydrogen production by water decomposition and manufacture this urge
The method of agent, and the method using the catalyst hydrogen manufacturing.
【Background technology】
With the development in the world, pollute on the earth increasingly severe, find out a kind of petroleum replacing the energy be badly in need of solve.Hydrogen
Gas is used as the most abundant energy of reserves on the earth, and safety, efficiently, cleaning.But hydrogen makes difficulty, govern hydrogen becomes
The development of fungible energy source.At present, the research in light hydrogen production by water decomposition direction becomes the focus of research.During photocatalytic hydrogen production by water decomposition
Need to use catalyst, and in prior art, the speed of catalyst hydrogen manufacturing is relatively low, it is impossible to meet the needs of hydrogen manufacturing.Develop high property
The photocatalytic hydrogen production by water decomposition of energy is with catalyst then into the key point of photocatalytic hydrogen production by water decomposition.
In the last few years, prepare hydrogen based on semiconductor light-catalyst and semiconductor composite to attract wide attention,
Wherein LDH (Layered Double Hydroxide, layered double hydroxide) material is used as catalysis material or multiple
Close semi-conducting material and obtain extensive research.LDH is the important anion type laminated clay material of a class, the divalence of laminate and
Trivalent metal cation is in laminate high degree of dispersion, and forms orderly agent structure with hydroxyl with covalent bond.Researcher passes through
Different types of metal ion is regulated and controled by rational design, and the hydrotalcite of synthesis imparts the multi-functional characteristic of such material.
Hydrotalcite is applied to the application and development that photochemical catalyzing field must promote catalysis material.And current LDH class materials
Unsatisfactory, such as number of patent application CN201110376582.X propositions applied by obtained catalyst in photochemical catalyzing field
A kind of photochemical catalyzing prepares stratiform houghite photocatalyst of hydrogen and preparation method thereof, and which adopts coprecipitation, synthesis
Serial light decomposition water prepares the stratiform hydrotalcite photochemical catalyst of hydrogen, and hydrogen-producing speed is only every gram of 0.314 mmoles of catalyst
You produce hydrogen effect unsatisfactory per hour (0.314mmol/h).
Therefore, how a kind of hydrogen production rate catalyst faster is provided, just into a kind of technical issues that need to address！
【Content of the invention】
For overcoming LDH classes material catalyst in the slow-footed technical barrier of photocatalytic hydrogen production by water decomposition, the invention provides
A kind of fireballing catalyst of smooth hydrogen production by water decomposition and the method for manufacturing the catalyst, and the method using the catalyst hydrogen manufacturing.
The present invention solves the scheme of technical problem and is to provide a kind of catalyst, and which is used for photocatalytic hydrogen production by water decomposition gas, its
It is C3N4The compound that doping Ni-Al-LDH is formed, Ni-Al-LDH and C in the compound3N4Mass ratio be 1：(1.5-
19).
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 °
Peak and (003) that has at 2 θ=11.4 °, 22.4 °, 35.0 ° and 62.0 ° of Ni-Al-LDH, (006), (009) and
(110) characteristic peak.
Preferably, the compound has in wave number 3150cm in infrared spectrum-1Transmission peaks.
The present invention also provides a kind of preparation method of catalyst, and which comprises the following steps：
By Ni-Al-LDH and C3N4In mass ratio 1：(1.5-19) mixed grinding, until described two materials are in powder；
Mixed-powder after by grinding adds solvent to form suspension；To suspension centrifugal treating, separator is obtained；Separator is dried
Obtain catalyst.
Preferably, need to be stirred when the mixed-powder forms suspension, stir speed (S.S.) is 800r/min-2000r/
Min, mixing time are 18h-36h.
Preferably, temperature when drying to the separator is 60 DEG C -100 DEG C, and drying time is 18h-36h.
The present invention also provides a kind of method of photocatalytic hydrogen production by water decomposition, it is characterised in that comprise the following steps：
Above-mentioned catalyst is inserted in the reactant liquor including water and methyl alcohol；Using wavelength 0nm-780nm light irradiation institute
State reactant liquor liquid to produce hydrogen.
Preferably, when irradiating described reactant liquor, while being stirred to the reactant liquor, and the temperature of reactant liquor is maintained
20℃-30℃.
Compared with prior art, catalyst composites of the invention are by adopting 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, make catalyst be provided simultaneously with the catalysis characteristics of two kinds of materials, and above-mentioned structure has been multiplied the urging of catalyst
Change function, with very high hydrogen-producing speed, can reach every gram of catalyst hydrogen output about 200mmol/g per hour, with simple Ni-
Al-LDH and C3N4Compare, hydrogen-producing speed is significantly improved.
Compared with prior art, manufacture catalyst of the invention is simple to manufacture, and will not produce chemical reaction, to environment without dirt
Dye, is only simple physical mixed, also embodies manufacture hydrogen, safeguard the objective of environmental nonpollution.
Compared with prior art, the catalyst hydrogen production process using the present invention is simple, and the speed of hydrogen manufacturing is high, greatly reduces
The cost of hydrogen manufacturing.
Simultaneously the reactant liquor is stirred during the light of the present invention irradiation 0nm-780nm, makes catalyst and reaction
Liquid mixing is more uniform, has further speeded up the speed of hydrogen manufacturing.
When the present invention irradiation ultraviolet light and/or visible ray simultaneously, 20 DEG C -30 DEG C of temperature in reactor is maintained, is protected
Reaction temperature has been demonstrate,proved, hydrogen manufacturing speed has been made faster.
【Description of the drawings】
Fig. 1 is the XRD (X-ray of the material Ni-Al-LDH (nickel aluminum bimetal hydroxide) of the catalyst of the manufacture present invention
Diffraction, X-ray diffraction) collection of illustrative plates.
Fig. 2 is the material C of the catalyst of the manufacture present invention3N4The XRD spectrum of (carbonitride).
Fig. 3 is the Ni-Al-LDH and C of the present invention3N4The XRD spectrum of three kind catalyst of the different quality than making after mixing.
Fig. 4 is that the present invention checks C using SEM (scanning electron microscope SEM)3N4
Microscopic appearance result schematic diagram.
Fig. 5 is the schematic diagram of 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 microscopes)
See the schematic diagram of the microscopic appearance result of catalyst.
Fig. 7 is the C of the present invention3N4Light absorpting ability measurement result schematic diagram.
Fig. 8 is the schematic diagram of the measurement result of the light absorpting ability of the Ni-Al-LDH of the present invention.
Fig. 9 is Ni-Al-LDH of the present invention and C3N4The measurement result of light absorpting ability of the catalyst that is compounded to form show
It is intended to.
Figure 10 be the present invention catalyst, C3N4Comparison diagram with the examination of infrared spectrum result of Ni-Al-LDH.
Figure 11 is the close-up schematic view of Figure 10.
Figure 12 is the schematic flow sheet of the method that the present invention prepares catalyst.
Figure 13 is schematic flow sheet of the present invention using the method for catalyst preparation hydrogen.
【Specific embodiment】
In order that the purpose of the present invention, technical scheme and advantage become more apparent, below in conjunction with accompanying drawing and embodiment,
The present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only in order to explain the present invention,
It is not intended to limit the present invention.
The catalyst of the present invention is in C3N4The compound that doping Ni-Al-LDH is formed, is denoted as Ni-Al-LDH/
C3N4.Ni-Al-LDH and C in compound3N4Mass ratio be preferably 1：(1.5-19).The mutual complex of doping latter two material
Into compound, but still keep the characteristic of layer structure, wherein Ni-Al-LDH is interspersed in C3N4In layer structure, which is to 0nm-
The light (ultraviolet light and visible ray) of 780nm has absorbability, and absorbability is very high, makes the efficiency of light hydrogen production by water decomposition notable
Improve.
Above-mentioned Ni-Al-LDH and C3N4Mass ratio be 1:When 9, compound is labeled as 10-LDH/90-C3N4, above-mentioned
Ni-Al-LDH and C3N4Mass ratio be 1:4 (i.e. 2:8), when, the compound that makes according to the method described above is labeled as 20-
LDH/80-C3N4, above-mentioned Ni-Al-LDH and C3N4Mass ratio be about 1:2.3 (i.e. 3:7), when, produce according to the method described above
The compound for coming is labeled as 30-LDH/70-C3N4.
Fig. 1, Fig. 2 and Fig. 3 is referred to, Fig. 1 is that the XRD to Ni-Al-LDH is characterized, and Fig. 2 is to C3N4XRD characterize, Fig. 3
It is to 10-LDH/90-C3N4, 20-LDH/80-C3N4And 30-LDH/70-C3N4The XRD of three kinds of compounds is characterized.To above-mentioned three kinds
The XRD of compound is characterized as can be seen that single-phase Ni-Al-LDH is respectively in 2 θ=11.4 °, 22.4 °, 35.0 °, 39.7 °,
46.5 °, the characteristic diffraction peak (003) of 62.0 ° of Ni-Al-LDHs for occurring in that corresponding with 72.8 °, (006), (009), (015),
(018), (110) and (116).Single-phase C3N4C is correspondingly occurred in that respectively 2 θ=13.04 ° and 27.47 °3N4(100) and
(002) characteristic diffraction peak, three kinds of complex catalysts all have C3N4(002) characteristic peak, while have corresponding to Ni-Al-
(003) of LDH, (006), (009) and (110) characteristic peak, and with the increase of Ni-Al-LDH contents in appropriate scope,
Intensity corresponding to the characteristic peak of Ni-Al-LDH increases therewith, illustrates there is C in above-mentioned complex catalyst3N4And Ni-Al-
There is no chemical change in LDH, this bi-material, also keep the starting substance.
It is C to see also Fig. 4 and Fig. 5, Fig. 43N4Microscopic appearance characterized using SEM, Fig. 5 is for Ni-Al-LDH
Microscopic appearance is characterized using SEM.As can be seen that C3N4Particle is by the layer structure of laminated structure accumulation, i.e. C3N4
It is to be stacked by the laminated structure that a large amount of particle diameters are 200nm or so is unordered, and laminated structure is equally have in large quantities more
Little laminated structure stacking is formed.Ni-Al-LDH is also the layer structure stacked by laminated structure, and the heap of laminated structure
Folded then follow certain rule, which is that the laminated structure for being about 100nm by thickness piles up shape together with essentially identical quantity
Into the stratiform monomer Cluster Structures that particle diameter is about 400nm.From analysis, analysis understands C3N4It is by different with Ni-Al-LDH
Layer structure is constituted.From design feature, as both materials are both with lamellar character, during doping also more
Contacting with each other and uniformly mix beneficial to bi-material.
Fig. 6 is referred to, Fig. 6 is C3N4The compound 20-LDH/80-C of doping Ni-Al-LDH3N4Microscopic appearance adopt
TEM is characterized, it can be seen that complex catalyst has layer structure under microcosmic, and the structure is unbodied.To the area
Domain carries out the result of electronic diffraction and can see that diffraction pattern does not have clearly diffraction ring, hence it is demonstrated that the region is unbodied
C3N4.Except unbodied C3N4, part high power regional transmission has obvious lattice, and corresponding at this is Ni-Al-LDH.Logical
Cross TEM and demonstrate C3N4Mutually it is combined with Ni-Al-LDH, still keeps stratiform to tie while also further demonstrating the composite
The characteristic of structure, Ni-Al-LDH is substantially uniform to be interspersed in C3N4Layer structure in.
Fig. 7, Fig. 8 and Fig. 9 is referred to, which respectively show single-phase Ni-Al-LDH and single-phase C3N4And both are compound
The complex catalyst 10-LDH/90-C of formation3N4The measure of light absorpting ability is carried out.As a result show, C3N4Not only to ultraviolet
Light (0nm<Wavelength<There is very strong absorbability 400nm), and to visible ray (400nm<Wavelength<780nm) also have stronger
Absorbability.And Ni-Al-LDH only has certain absorbability to ultraviolet light, and absorption region is very narrow, only in wavelength<
The region of 250nm has stronger absorbability.And compound 10-LDH/90-C3N4Two kind single-phase materials have then effectively been 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. its light (ultraviolet light and visible ray) to 0nm-780nm have absorbability, and absorbability is very high, compound 10-
LDH/90-C3N4It is bi-material at two to three times of ultraviolet light wave band absorbability sum in the absorbability of ultraviolet light wave band,
It is bi-material at four to five times of visible light wave range absorbability sum in the absorbability of visible light wave range, is therefore adopting
During the complex catalyst hydrogen manufacturing of the present invention, preferably irradiating ultraviolet light and/or visible ray.Angle from light absorpting ability is further
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
Transfer rate, increase electron-hole separative efficiency, fundamentally enhance C3N4Photocatalytic activity.
Refer to Figure 10 and Figure 11, Figure 10 and Figure 11 is 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
Can be seen that Ni-Al-LDH possesses the typical transmission peaks of layered double hydroxide class material, wherein wave number 3353cm-1With
1639cm-1Transmission peaks corresponded to the flexural vibrations of O-H in layered double hydroxide material, and wave number 1349cm-1Then right
Anion that should be in layered double hydroxide intercalation vibrates.For single-phase C3N4, which is in wave number 3150cm-1Transmission
Peak also corresponds to the flexural vibrations of O-H, and these O-H come from C3N4The hydrone of absorption.Preparation method system using above-mentioned doping
The transmission peaks of standby three kinds of complex catalysts out and single-phase C3N4Substantially completely overlap, compound also has in infrared spectrum
Have in wave number 3150cm-1Transmission peaks, it is relatively low that this is attributed to Ni-Al-LDH contents in the composite, while also demonstrating
During whole doping, C3N4Its basic structure is maintained well.Although on the other hand also illustrate that the compound after doping is urged
The performance of agent has and is obviously improved, but C3N4Structure do not change substantially, Ni-Al-LDH as doping partly lead
Body material, with material of main part C3N4Close layer structure, this reduce bulk catalyst C to a certain extent3N4And visitor
Estrangement between body doped catalyst Ni-Al-LDH, Ni-Al-LDH and C3N4Between mix more thorough.
Figure 12 is referred to, the present invention also provides a kind of method for preparing the catalyst, the preparation method of the catalyst
Comprise the following steps：
Step S1：By Ni-Al-LDH and C3N4In mass ratio 1：(1.5-19) mixed grinding, until described two materials are in
Powder；
Step S2：Mixed-powder after by grinding adds solvent to form suspension；
Step S3：To suspension centrifugal treating, separator is obtained；
Step S4：Separator is dried to obtain catalyst.
When carrying out step S1, the Ni-Al-LDH and C of employing3N4Mass 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, stir speed (S.S.) during stirring is preferably
For more than 800r/min, more preferably preferably 800r/min-2000r/min, 1000r/min-2000r/min, stirring
Time preferably more than 18h, more preferably preferably 18h-36h, 24h-36h preferably adopt agitator during stirring,
Preferably magnetic stirring apparatus, can make stirring more uniform.Solvent used and Ni-Al-LDH and C3N4Immiscible, preferred solvents
Using other water such as deionized water, mountain spring water, mineral water, running water, preferably deionized water.
When carrying out step S4, freeze-day with constant temperature when drying, is preferably carried out, dry temperature is preferably 60 DEG C -100 DEG C, more preferably
For 70 DEG C -90 DEG C, preferably 80 DEG C, dry time is preferably more than 18h, preferably 18h-36h, more preferably
24h-36h.
There is Photocatalyzed Hydrogen Production gas efficiency high by catalyst obtained in the method.
Figure 13 is referred to, the present invention also provides a kind of method using the catalyst preparation hydrogen, concrete preparation process
Comprise the following steps：
Step T1：Above-mentioned catalyst is inserted in the reactant liquor including water and methyl alcohol；
Step T2：Adopt reactant liquor described in light irradiation of the wavelength in 0nm-780nm to produce hydrogen.
In step T1, the volume ratio of water and methyl alcohol in the reactant liquor is preferably (1.5-9):1, more preferably
For (3-5)：1, preferably 4:1, the water is deionized water, mountain spring water, other any kind of water such as running water, mineral water,
Preferably deionized water.It is appreciated that the amount of above-mentioned catalyst can be added in reactant liquor according to conventional ratio, namely catalyst
Amount ratio with reactant liquor is preferably 1g:(500-6000) ml, preferably 1g：(1000-3000) ml, more preferably
1g:2000ml.
In step T2, when irradiating to described reactant liquor, preferably, maintaining 20 DEG C -30 of temperature in reactor
DEG C, more preferably temperature is 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 is preferably adopted
Xe-Hg lamps.Preferably, when irradiating to described reactant liquor, while being stirred to the reactant liquor, stir speed (S.S.) is preferably
200r/min-500r/min, more preferably 250r/min-400r/min, preferably 300r/min.As a kind of deformation, can be with
First start to stir, then irradiate the light of 0nm-780nm.As another kind of deformation, the light of 0nm-780nm can be first irradiated, then is carried out
Stirring.
As a kind of selection, in step T1, the reactant liquor for adding catalyst is inserted in container, and to the appearance
Device is repeatedly vacuumized to be operated with filling with inert gas, then carries out step T2.The reactor is preferably closed container, excellent
Elect Pyrex glass reactor as.This step is carried out, the incoherent gas for not affecting to measure hydrogen in reactor can be made,
Can be to being determined with the hydrogen output of catalyst hydrogen manufacturing in detail.
In order to be further detailed to the catalyst, the specific experiment group being listed below and contrast groups.
Experimental group 1：
Make catalyst：
The C of the Ni-Al-LDH and 2g of 0.5g is 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 powder；
The product of powder is placed in beaker, the deionized water for adding 50ml forms suspension, and uses magnetic stirring apparatus
It is stirred, mixing speed is 1000r/min, and mixing time is 24h；
With centrifuge to stirring after suspension process, obtain separator；
Separator is dried 24h in 80 DEG C of thermostatic drying chambers, the article for obtaining is catalyst.
Checking catalysis activity (using catalyst preparation hydrogen)：
The catalyst 50mg that precise is made, is then dissolved in 100ml reactant liquors, and reactant liquor is put
Enter Pyrex glass reactor, the reactant liquor is made up of 80ml deionized waters and 20ml methyl alcohol, i.e. deionized water and methyl alcohol
Volume ratio is 4:1；
Pyrex glass reactor is carried out 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 all the time, and to added with catalyst reactant liquor keep with
The rotating speed of 300r/min keeps continuously stirring, and adopts the Xe-Hg lamps of power position 880w using visible-ultraviolet irradiation light source
(Newport, RI) is incident from reactor top, and filters the infrared light in incident light source using Circulated water filter, with
Guarantee that incident light is ultraviolet light and visible ray；
And after starting from photochemical catalyzing reaction, form and aspect collection of illustrative plates is automatically anti-to Pyrex glass as chronomere with 1h
Answer gas in device to be sampled, analyze hydrogen content therein and keep a record.
With 20h as an evaluation cycle, light source is closed when reaction carries out 20h, stop reaction, anti-to Pyrex glass
Device is answered to be vacuumized for several times and filling with inert gas, until remaining without a upper evaluation cycle in Pyrex glass reactor
Hydrogen.When determining whether hydrogen, the gas in Pyrex glass reactor is examined preferably by form and aspect collection of illustrative plates
Survey.
Then light source is opened, is started the evaluation cycle of new 20h, is carried out four evaluation cycles altogether.
Experimental group 2：
When making catalyst, the C of the Ni-Al-LDH and 2.25g of 0.25g is weighed respectively3N4, i.e. Ni-Al-LDH and C3N4Matter
Amount is than being 1:9, and grind in corundum mortar, until described two materials are in powder；Other conditions and the experiment of 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 is weighed respectively3N4, i.e. Ni-Al-LDH and C3N4's
Mass ratio is 1:2.3, and grind in corundum mortar, until described two materials are in powder；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 is weighed respectively3N4, i.e. Ni-Al-LDH and C3N4
Mass ratio be 1:19, and grind in corundum mortar, until described two materials are in powder；Other conditions and experimental group 1
Experiment condition identical.
Experimental group 5：
When making catalyst, the C of the Ni-Al-LDH and 1.5g of 1g is weighed respectively3N4, i.e. Ni-Al-LDH and C3N4Quality
Than for 1:1.5, and grind in corundum mortar, until described two materials are in powder；Other conditions and the experiment of experimental group 1
Condition is identical.
Experimental group 6：
When making catalyst, the product of powder is placed in beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed is 800r/min, and mixing time is 24h；Other conditions and the experiment of experimental group 1
Condition is identical.
Experimental group 7：
When making catalyst, the product of powder is placed in beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed is 1000r/min, and mixing time is 18h；Other conditions and the reality of experimental group 1
Test condition identical.
Experimental group 8：
When making catalyst, separator is dried 24h in 60 DEG C of thermostatic drying chambers, the article for obtaining is catalyst；
Other conditions are identical with the experiment condition of experimental group 1.
Experimental group 9：
When making catalyst, separator is dried 24h in 100 DEG C of thermostatic drying chambers, the article for obtaining is catalyst；
Other conditions are identical with the experiment condition of experimental group 1.
Experimental group 10：
When making catalyst, separator is dried 18h in 800 DEG C of thermostatic drying chambers, the article for obtaining is catalyst；
Other conditions are identical with the experiment condition of experimental group 1.
Experimental group 11：
During checking catalysis activity, then the catalyst 50mg that precise is made is dissolved in 100ml reactant liquors
In, and reactant liquor is inserted Pyrex glass reactor, the reactant liquor is made up of 60ml deionized waters and 40ml methyl alcohol, i.e.,
Deionized water and methyl alcohol volume ratio are 1.5:1；Other conditions are identical with the experiment condition of experimental group 1.
Experimental group 12：
During checking catalysis activity, then the catalyst 50mg that precise is made is dissolved in 100ml reactant liquors
In, and reactant liquor is inserted Pyrex glass reactor, the reactant liquor is made up of 90ml deionized waters and 10ml methyl alcohol, i.e.,
Deionized water and methyl alcohol volume ratio are 9:1；Other conditions are identical with the experiment condition of experimental group 1.
Experimental group 13：
During checking catalyst activity, Pyrex glass temperature of reactor is maintained 25 DEG C all the time, and to added with catalysis
The reactant liquor of agent keeps keeping continuously stirring with the rotating speed of 200r/min, and adopts power position using visible-ultraviolet irradiation light source
The Xe-Hg lamps (Newport, RI) of 880w are incident from reactor top, and using Circulated water filter by incident light source
Infrared light is filtered, to guarantee incident light as ultraviolet light and visible ray；Other conditions are identical with the experiment condition of experimental group 1.
Experimental group 14：
During checking catalyst activity, Pyrex glass temperature of reactor is maintained 25 DEG C all the time, and to added with catalysis
The reactant liquor of agent keeps keeping continuously stirring with the rotating speed of 500r/min, and adopts power position using visible-ultraviolet irradiation light source
The Xe-Hg lamps (Newport, RI) of 880w are incident from reactor top, and using Circulated water filter by incident light source
Infrared light is filtered, to guarantee incident light as ultraviolet light and visible ray；Other conditions are identical with the experiment condition of experimental group 1.
Experimental group 15：
During checking catalyst activity, Pyrex glass temperature of reactor is maintained 20 DEG C all the time, and to added with catalysis
The reactant liquor of agent keeps keeping continuously stirring with the rotating speed of 300r/min, and adopts power position using visible-ultraviolet irradiation light source
The Xe-Hg lamps (Newport, RI) of 880w are incident from reactor top, and using Circulated water filter by incident light source
Infrared light is filtered, to guarantee incident light as ultraviolet light and visible ray；Other conditions are identical with the experiment condition of experimental group 1.
Experimental group 16：
During checking catalyst activity, Pyrex glass temperature of reactor is maintained 30 DEG C all the time, and to added with catalysis
The reactant liquor of agent keeps keeping continuously stirring with the rotating speed of 300r/min, and adopts power position using visible-ultraviolet irradiation light source
The Xe-Hg lamps (Newport, RI) of 880w are incident from reactor top, and using Circulated water filter by incident light source
Infrared light is filtered, to guarantee incident light as ultraviolet light and visible ray；Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 1：
Directly used using Ni-Al-LDH as catalyst applications, other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 2：
Directly with C3N4Use as catalyst applications, other conditions are identical with 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 is weighed respectively3N4, Ni-Al-LDH and C3N4Press matter
Amount is than being 1:24 ratio mixing, and grind in corundum mortar, until described two materials are in powder；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 is weighed respectively3N4, Ni-Al-LDH and C3N4Press
Mass ratio is 1:1 ratio mixing, and grind in corundum mortar, until described two materials are in powder；Other conditions with
The experiment condition of experimental group 1 is identical.
Contrast groups 5：
When making catalyst, the product of powder is placed in beaker, adds the deionized water of 50ml, and use magnetic agitation
Device is stirred, and mixing speed is 600r/min, and mixing time is 24h；Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 6：
When making catalyst, the product of powder is placed in beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed is 1500r/min, and mixing time is 24h；Other conditions and the reality of experimental group 1
Test condition identical.
Contrast groups 7：
When making catalyst, the product of powder is placed in beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed is 1000r/min, and mixing time is 15h；Other conditions and the reality of experimental group 1
Test condition identical.
Contrast groups 8：
When making catalyst, the product of powder is placed in beaker, the deionized water for adding 50ml forms suspension, and
It is stirred with magnetic stirring apparatus, mixing speed is 1000r/min, and mixing time is 30h；Other conditions and the reality of experimental group 1
Test condition identical.
Contrast groups 9：
When making catalyst, separator is dried 24h in 50 DEG C of thermostatic drying chambers, the article for obtaining is catalyst；
Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 10：
When making catalyst, separator is dried 24h in 110 DEG C of thermostatic drying chambers, the article for obtaining is catalyst；
Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 11：
When making catalyst, separator is dried 15h in 80 DEG C of thermostatic drying chambers, the article for obtaining is catalyst；
Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 12：
When making catalyst, separator is dried 30h in 80 DEG C of thermostatic drying chambers, the article for obtaining is catalyst；
Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 13：
During checking catalysis activity, then the catalyst 50mg that precise is made is dissolved in 100ml reactant liquors
In, and reactant liquor is inserted Pyrex glass reactor, the reactant liquor is made up of 50ml deionized waters and 50ml methyl alcohol, i.e.,
Deionized water and methyl alcohol volume ratio are 1:1；Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 14：
During checking catalysis activity, then the catalyst 50mg that precise is made is dissolved in 100ml reactant liquors
In, and reactant liquor is inserted Pyrex glass reactor, the reactant liquor is made up of 95ml deionized waters and 5ml methyl alcohol, i.e.,
Deionized water and methyl alcohol volume ratio are 19:1；Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 15：
During checking catalyst activity, Pyrex glass temperature of reactor is maintained 25 DEG C all the time, and to added with catalysis
The reactant liquor of agent keeps keeping continuously stirring with the rotating speed of 100r/min, and adopts power position using visible-ultraviolet irradiation light source
The Xe-Hg lamps (Newport, RI) of 880w are incident from reactor top, and using Circulated water filter by incident light source
Infrared light is filtered, to guarantee incident light as ultraviolet light and visible ray；Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 16：
During checking catalyst activity, Pyrex glass temperature of reactor is maintained 25 DEG C all the time, and to added with catalysis
The reactant liquor of agent keeps keeping continuously stirring with the rotating speed of 700r/min, and adopts power position using visible-ultraviolet irradiation light source
The Xe-Hg lamps (Newport, RI) of 880w are incident from reactor top, and using Circulated water filter by incident light source
Infrared light is filtered, to guarantee incident light as ultraviolet light and visible ray；Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 17：
During checking catalyst activity, Pyrex glass temperature of reactor is maintained 10 DEG C all the time, and to added with catalysis
The reactant liquor of agent keeps keeping continuously stirring with the rotating speed of 300r/min, and adopts power position using visible-ultraviolet irradiation light source
The Xe-Hg lamps (Newport, RI) of 880w are incident from reactor top, and using Circulated water filter by incident light source
Infrared light is filtered, to guarantee incident light as ultraviolet light and visible ray；Other conditions are identical with the experiment condition of experimental group 1.
Contrast groups 18：
During checking catalyst activity, Pyrex glass temperature of reactor is maintained 40 DEG C all the time, and to added with catalysis
The reactant liquor of agent keeps keeping continuously stirring with the rotating speed of 300r/min, and adopts power position using visible-ultraviolet irradiation light source
The Xe-Hg lamps (Newport, RI) of 880w are incident from reactor top, and using Circulated water filter by incident light source
Infrared light is filtered, to guarantee incident light as ultraviolet light and visible ray；Other conditions are identical with the experiment condition of experimental group 1.
Experimental result：As shown in Table 1 and Table 2.
Different condition contrast 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), stirs
The unit for mixing the time is hour (h), and the unit of baking temperature is degree Celsius (DEG C), and the unit of drying time is hour (h).
Different condition contrast situation table during the checking catalyst activity of table 2
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 is maintained all the time, the unit of reaction temperature is degree Celsius (DEG C), the unit of hydrogen output for mM/per gram of catalysis
Agent (mmol/gcat).
Tie from the experiment 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 understands, in the component of the catalyst of the present 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.
Knowable to the experimental result comparative analysis of experimental group 1, experimental group 6, contrast groups 5 and contrast groups 6, the preparation of the present invention
The agitation phases of catalyst, when mixing speed is more than 1000r/min, mixing speed change is had not significant impact to hydrogen output greatly,
Therefore mixing speed preferably more than 800r/min, preferably more preferably 800r/min-2000r/min, 1000r/min-
2000r/min.
Knowable to the experimental result comparative analysis of experimental group 1, experimental group 7, contrast groups 7 and contrast groups 8, the preparation of the present invention
The agitation phases of catalyst, upon agitation between more than 24h, mixing time is elongated to be had not significant impact to hydrogen output, thus stirring when
Between be preferably more than 18h, more preferably 18h-36h, preferably 24h-36h.
Knowable to the experimental result comparative analysis of experimental group 1, experimental group 8, experimental group 9, contrast groups 9 and contrast groups 10,
The centrifugal drying stage for preparing catalyst of the present invention, baking temperature are preferably 60 DEG C -100 DEG C, more preferably 70 DEG C -90
DEG C, preferably 80 DEG C.
Knowable to the experimental result comparative analysis of experimental group 1, experimental group 10, contrast groups 11 and contrast groups 12, the present invention
The centrifugal drying stage for preparing catalyst, when drying between more than 24h, drying time is elongated not to have obvious shadow to hydrogen output
Ring, therefore drying time preferably more than 18h, preferably more preferably 18h-36h, 24h-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 speed is：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 C3N4Make 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 as can be seen that the present invention's uses catalysis
When agent prepares hydrogen, the ratio of water and methyl alcohol in reactant liquor used is preferably (1.5-9)：1, preferably (3-5)：1, enter
One step is preferably 4:1.
From test group 1, experimental group 13, experimental group 14, contrast groups 15 and contrast groups 16 as can be seen that the present invention's uses catalysis
When agent prepares hydrogen, during to the reactant liquor irradiating ultraviolet light in the reactor and/or visible ray, while entering to the reactant liquor
Row stirring, stir speed (S.S.) 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 as can be seen that the present invention's uses catalysis
When agent prepares hydrogen, during to the reactant liquor irradiating ultraviolet light in the reactor and/or visible ray, 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 adopting 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, make catalyst be provided simultaneously with the catalysis characteristics of two kinds of materials, and above-mentioned structure has been multiplied the urging of catalyst
Change function, with very high hydrogen-producing speed, can reach every gram of catalyst hydrogen output about 200mmol/g per hour, with simple Ni-
Al-LDH and C3N4Compare, hydrogen-producing speed is significantly improved.
Compared with prior art, manufacture catalyst of the invention is simple to manufacture, and will not produce chemical reaction, to environment without dirt
Dye, is only simple physical mixed, also embodies manufacture hydrogen, safeguard the objective of environmental nonpollution.
Compared with prior art, the catalyst hydrogen production process using the present invention is simple, and the speed of hydrogen manufacturing is high, greatly reduces
The cost of hydrogen manufacturing.
Simultaneously the reactant liquor is stirred when the present invention irradiation ultraviolet light and/or visible ray, make catalyst and
Reactant liquor mixing is more uniform, has further speeded up the speed of hydrogen manufacturing.
When the present invention irradiation ultraviolet light and/or visible ray simultaneously, 20 DEG C -30 DEG C of temperature in reactor is maintained, is protected
Reaction temperature has been demonstrate,proved, hydrogen manufacturing speed has been made faster.
Presently preferred embodiments of the present invention is the foregoing is only, not in order to limit the present invention, all in original of the invention
Any modification that is made within then, equivalent and improvement etc. all should include within protection scope of the present invention.
Claims (10)
1. a kind of catalyst, which is used for photocatalytic hydrogen production by water decomposition gas, it is characterised in that：The catalyst is in C3N4Doping Ni-
The compound that Al-LDH is formed, Ni-Al-LDH and C in the compound3N4Mass ratio be 1：(1.5-19).
2. catalyst as claimed in claim 1, it is characterised in that：The compound is layer structure, and wherein Ni-Al-LDH wears
It is inserted in C3N4In layer structure.
3. catalyst as claimed in claim 1, it is characterised in that：The compound has absorption energy to the light of 0nm-780nm
Power.
4. catalyst as claimed in claim 1, it is characterised in that：The X-ray diffraction of the compound has C simultaneously3N4?
(002) characteristic peak and the tool at 2 θ=11.4 °, 22.4 °, 35.0 ° and 62.0 ° of Ni-Al-LDH that 2 θ=27.47 ° have
(003) having, (006), (009) and (110) characteristic peak.
5. catalyst as claimed in claim 1, it is characterised in that：The compound has in wave number 3150cm in infrared spectrum-1Transmission peaks.
6. a kind of preparation method of catalyst, it is characterised in that comprise the following steps：
By Ni-Al-LDH and C3N4In mass ratio 1：(1.5-19) mixed grinding, until described two materials are in powder；To grind
Mixed-powder after mill adds solvent to form suspension；To suspension centrifugal treating, separator is obtained；Separator is dried to obtain
Catalyst.
7. the preparation method of catalyst as claimed in claim 6, it is characterised in that：The mixed-powder is needed when forming suspension
It is stirred, stir speed (S.S.) is 800r/min-2000r/min, and mixing time is 18h-36h.
8. the preparation method of catalyst as claimed in claim 6, it is characterised in that：Temperature when drying to the separator is
60 DEG C -100 DEG C, drying time is 18h-36h.
9. a kind of method of photocatalytic hydrogen production by water decomposition, it is characterised in that comprise the following steps：
Catalyst described in claim 1 is inserted in the reactant liquor including water and methyl alcohol；Using wavelength 0nm-780nm light
Irradiate the reactant liquor liquid to produce hydrogen.
10. the method for photocatalytic hydrogen production by water decomposition as claimed in claim 9, it is characterised in that：When irradiating described reactant liquor,
Simultaneously the reactant liquor is stirred, and maintains 20 DEG C -30 DEG C of the temperature of reactant liquor.
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