CN104959153B - The preparation method and application of Photocatalyzed Hydrogen Production auxiliary agent, photochemical catalyst and photochemical catalyst - Google Patents
The preparation method and application of Photocatalyzed Hydrogen Production auxiliary agent, photochemical catalyst and photochemical catalyst Download PDFInfo
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- CN104959153B CN104959153B CN201510308310.4A CN201510308310A CN104959153B CN 104959153 B CN104959153 B CN 104959153B CN 201510308310 A CN201510308310 A CN 201510308310A CN 104959153 B CN104959153 B CN 104959153B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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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Abstract
The present invention provides a kind of novel photocatalysis production hydrogen auxiliary agent, and the Photocatalyzed Hydrogen Production auxiliary agent is nano lamellar NiMoS, and the photochemical catalyst of CdS@NiMoS helical structures is formed by the bar-shaped CdS major catalysts of modification one-dimensional.The preparation method of the photochemical catalyst realizes the synthesis of spiral compound nanometer photocatalyst by two step hydrothermal techniques, has synthesized size uniform, the CdS nanometer rods of pattern rule in ethylenediamine system first, has then made Na by hydro-thermal pressurization2MoO4、Ni(NO3)2Laminate sulfide NiMoS corresponding to thiocarbamide reaction synthesis, and form heterojunction structure CdS NiMoS with nano bar-shape CdS.The catalyst shows excellent Photocatalyzed Hydrogen Production performance, and seawater hydrogen manufacturing yield is up to 19.147 mmolg‑1·h‑1, new catalyst Research idea is provided for new energy development.
Description
Technical field
The invention belongs to catalysis material technical field, relate in particular to it is a kind of be applied to photocatalysis Decomposition distilled water with
And the co-catalyst NiMoS of natural sea-water hydrogen manufacturing and major catalyst CdS nanorod shapeds are into spiral composite Nano metal sulfide light
Catalyst and its preparation method and application.
Background technology
Photocatalysis solar energy is converted into can be significant by the fuel of human use.Hydrogen is wide as a kind of application
General raw material, greatly effect is played in terms of synthesis ammonia and carbon dioxide conversion are methanol and hydrocarbon.Day simultaneously
Right seawater has huge prospect as a kind of inexhaustible natural resources, its development and utilization.Therefore half is utilized
Conductor photochemical catalyst decomposing water with solar energy hydrogen manufacturing causes extensive concern both domestic and external.
Visible light-responded catalyst of the research allotment with appropriate band position be improve visible light catalytic hydrogen generation efficiency,
The research emphasis for promoting photocatalysis technology further to develop.
The content of the invention
The present invention provides the preparation method of a kind of new and effective Photocatalyzed Hydrogen Production auxiliary agent, photochemical catalyst and photochemical catalyst and answered
With, the hydrogen production efficiency using sunshine is not only greatly improved, and seawater hydrogen manufacturing can be made full use of, exploitation and profit to new energy
With significant.
In order to solve the above technical problems, the present invention is achieved using following technical scheme：
On the one hand, the present invention provides a kind of novel photocatalysis production hydrogen auxiliary agent, and the Photocatalyzed Hydrogen Production auxiliary agent is composite Nano layer
Shape, chemical formula NiMoS.
On the other hand, present invention offer is a kind of modifies the photochemical catalyst to be formed by Photocatalyzed Hydrogen Production auxiliary agent NiMoS, the light
Catalyst is the helical structure that the formation of one-dimensional rod-like CdS major catalysts surface is coated on by Photocatalyzed Hydrogen Production auxiliary agent NiMoS, is changed
Learn expression formula：CdS@NiMoS.The bar-shaped CdS major catalysts of NiMoS modification one-dimensionals form the helical structure combined closely.
Laminar nano MoS2Two-dimensional structure with similar graphene, it is auxiliary agent excellent in photolysis water hydrogen reaction, its
Specific surface area is huge, can provide more reaction active sites；Its band gap locations and band gap width match with CdS nanometer rods, can
Effectively it is compounded to form heterojunction structure；The a large amount of unsaturated sulphur atom of its layer structure marginal existence, the system of catalyst can be greatly improved
Hydrogen performance.In MoS2Marginal position introduces Ni ions and regulated and controled, and forms NiMoS layer structures, further improves photocatalysis production
Hydrogen efficiency.
Another further aspect, the present invention provide a kind of preparation method of photochemical catalyst, comprised the following steps：
（1）Utilize solvent structure photocatalysis major catalyst CdS nanometer rods；
（2）Utilize hydro-thermal method synthesis photocatalysis auxiliary agent and the compound catalyst CdS@NiMoS of major catalyst.
Further, preparation process is specific as follows：
（1）CdS presoma Cd (S2CNEt2)2Preparation：By cadmium nitrate Cd (NO3)2·4H2O and DDTC (NaS2CNEt2·
3H2O, NaDDTC) press 1:2 mol ratio is dissolved in suitable quantity of water respectively, then under magnetic stirring that the DDTC aqueous solution is slow
It is added dropwise to Cd (NO3)2In the aqueous solution, that is, obtain CdS presomas Cd (DDTC)2, product is washed and is dried in vacuo；
（2）The preparation of CdS nanometer rods：Ethylenediamine is added in autoclave to the 70-80% of its volume, is then added thereto
Cd(DDTC)2, it is reacted into 6-48 h at 120-200 DEG C, that is, obtains CdS nanometer rods, product is washed and is dried in vacuo；
（3）It is prepared by CdS@NiMoS hydro-thermal method：80-150 mg are added in the beaker containing 15-25 mL distilled water
CdS nanometer rods, and it is another containing the beaker of 15-25 mL distilled water in be separately added into Na2MoO4、Ni(NO3)2With enough sulphur
Urea, control auxiliary agent NiMoS and CdS proportion are in 0.01-0.25:1；Mixed after reactant ultrasonic decomposition in beaker equal
It is even, mixed liquor is transferred in autoclave, 5-25 h are reacted at 180-220 DEG C；CdS NiMoS helical structures are obtained to answer
Catalyst is closed, product is washed and is dried in vacuo.
Wherein, the source of each element in auxiliary agent NiMoS is Ni (NO respectively3)2、Na2MoO4And thiocarbamide,
The amount of material in the amount and final products of Ni, Mo material is consistent, and thiocarbamide is sulphur source.
Preparation method of the present invention has technique simple, and cost is cheap, it is reproducible the characteristics of, can prepare composition it is controllable,
The sunshine hydrogen production photocatalyst of performance efficiency.
Application of above-mentioned photochemical catalyst and the Photocatalyzed Hydrogen Production auxiliary agent in terms of photocatalysis hydrogen production.
Application of above-mentioned photochemical catalyst and the Photocatalyzed Hydrogen Production auxiliary agent in terms of photocatalysis natural sea aquatic products hydrogen, it is possible to achieve right
The development and utilization of marine resources.
Above-mentioned visible light catalytic auxiliary agent has good application effect in terms of simulated solar irradiation hydrogen manufacturing.It is to meet new energy to need
The novel photocatalysis material asked.The Photocatalyzed Hydrogen Production auxiliary agent can increase substantially the Photocatalyzed Hydrogen Production performance of major catalyst, and this is helped
The expression formula of novel photocatalyst is CdS@NiMoS obtained by agent modification major catalyst.
The light H2-producing capacity of the novel nano Photocatalyzed Hydrogen Production auxiliary agent NiMoS compound primary catalysts CdS nanometer rods of the present invention
Research, method are as follows：
10-50 mg photochemical catalysts are weighed, is dispersed in 40-80 mL distilled water, is then respectively adding Na2SO3With
Na2S under magnetic stirring, by the use of 300 W xenon lamps as visible light source, carries out photo-reduction water decomposition production as photocatalysis sacrifice agent
Hydrogen is tested, and reacting space same time carries out a test sample, and every kind of sample is carried out continuously 3-5 production hydrogen analysis, uses gas-chromatography
Qualitative analysis is carried out, determines the content of product.Reaction reclaims catalyst after terminating.
Therefore, the present invention is based on hydro-thermal solvent-thermal method integrated reacting, by adjusting the species of different presomas and adding
Enter ratio, realize the composition regulation and control of new light production hydrogen co-catalyst.The preparation of catalyst is using the integration of hydro-thermal solvent-thermal method
The technology of synthesis：Size uniform has been synthesized in ethylenediamine system first, the CdS nanometer rods of pattern rule, has then passed through hydro-thermal
Environment makes Na2MoO4、Ni(NO3)2To the thiocarbamide reaction corresponding laminate sulfide NiMoS of synthesis, and formed with nano bar-shape CdS different
Matter structure.
Catalyst prepared by the present invention has stronger visible absorption, and solar energy utilization ratio is greatly improved,
Very high Activity and stabill is shown in terms of simulated solar irradiation hydrogen manufacturing, and excellent properties are shown in seawater hydrogen manufacturing.These
Feature shows that such catalyst has higher application value in new energy development field.
The heterojunction structure composition metal sulfide photocatalyst most preferably forms：Mo optimum load amount is 15%,
It is expressed as CdS@15%MoS2；Ni optimum load amount is 1%, is expressed as CdS@1%NiMoS.Complex light is urged made from the above method
Additive dosage in agent is had verified that as optimum proportioning, i.e., finds MoS on CdS nanorod foundations first2Optimal production
Hydrogen load capacity；Optimizing MoS2On the basis of dosage, the additional proportion for adjusting Ni ions is imitated with obtaining optimal photocatalysis hydrogen production
The CdS@NiMoS composite photo-catalysts of fruit.Above-mentioned catalyst combines the characteristic of different semiconductors, and the compound of various sulfide makes
The composite catalyst has suitable position of energy band；Meanwhile the unsaturated sulfide linkage and helical structure at catalysis material edge can provide
A large amount of avtive spots, be advantageous to hydrogen ion adsorption, therefore be the NEW TYPE OF COMPOSITE catalysis material with excellent properties.
Compared with prior art, the advantages and positive effects of the present invention are：The present invention is prepared by the hydro-thermal reaction of simplicity
Helical structure novel photocatalysis produces hydrogen auxiliary agent composite nanoparticle, and is efficiently applied to the hydrogen manufacturing of photodissociation distilled water and photolysis of seawater system
Hydrogen, particularly photolysis of seawater hydrogen manufacturing application prospect are extensive.
Brief description of the drawings
Fig. 1 is that novel photocatalysis prepared by embodiment 1-3 produces CdS@obtained by hydrogen auxiliary agent NiMoS modification CdS major catalysts
NiMoS and traditional catalyst CdS and CdS@MoS2Scanning electron microscope sem photo comparison；
Fig. 2 is that novel photocatalysis prepared by embodiment 2-3 produces CdS@obtained by hydrogen auxiliary agent NiMoS modification CdS major catalysts
NiMoS and traditional catalyst CdS@MoS2Transmission electron microscope TEM photo comparisons；
Fig. 3 is that novel photocatalysis prepared by embodiment 1-4 produces CdS@obtained by hydrogen auxiliary agent NiMoS modification CdS major catalysts
NiMoS and traditional catalyst CdS and CdS@MoS2Simulated solar irradiation hydrogen manufacturing productivity ratio relatively scheme；
Fig. 4 is that novel photocatalysis prepared by embodiment 3 produces CdS@NiMoS obtained by hydrogen auxiliary agent NiMoS modification CdS major catalysts
The productivity ratio of the hydrogen manufacturing of photodissociation distilled water and photolysis of seawater hydrogen manufacturing is relatively schemed respectively；
Fig. 5 is that novel photocatalysis prepared by embodiment 3 produces CdS@NiMoS obtained by hydrogen auxiliary agent NiMoS modification CdS major catalysts
Photocatalysis hydrogen production stability test figure；
Fig. 6 is that novel photocatalysis prepared by embodiment 3 produces CdS@NiMoS obtained by hydrogen auxiliary agent NiMoS modification CdS major catalysts
X-ray diffraction before and after Photocatalyzed Hydrogen Production（XRD）Figure；
Fig. 7 is that novel photocatalysis prepared by embodiment 3 produces CdS@NiMoS obtained by hydrogen auxiliary agent NiMoS modification CdS major catalysts
SEM photograph before and after Photocatalyzed Hydrogen Production.
Embodiment
In view of the deficiencies of the prior art, the present invention provides the preparation of CdS@NiMoS sunshine hydrogen manufacturing nano-photocatalysts
Method.
The visible optical drive catalyst of the present invention is by co-catalyst（NiMoS）With major catalyst（CdS）Form, pass through hydro-thermal
Solvent-thermal method is by this several semiconductors coupling.
（1）CdS presoma Cd (S2CNEt2)2Preparation：By cadmium nitrate Cd (NO3)2·4H2O and DDTC (NaS2CNEt2·
3H2O, DDTC) press 1:2 mol ratio is dissolved in suitable quantity of water respectively, then under magnetic stirring slowly drips the DDTC aqueous solution
Add to Cd (NO3)2In the aqueous solution, that is, obtain CdS presomas Cd (DDTC)2, product is washed and is dried in vacuo；
（2）The preparation of CdS nanometer rods：Ethylenediamine is added in autoclave to the 70-80% of its volume, is then added thereto
Cd(DDTC)2, it is reacted into 6-48 h at 120-200 DEG C, that is, obtains CdS nanometer rods, product is washed and is dried in vacuo；
（3）It is prepared by CdS@NiMoS hydro-thermal method：80-150mgCdS is added in the beaker containing 15-25 mL distilled water
Nanometer rods, and it is another containing the beaker of 15-25 mL distilled water in be separately added into Na2MoO4、Ni(NO3)2With enough thiocarbamides, control
Auxiliary agent NiMoS and CdS processed proportion is in 0.01-0.25:1；Reactant in beaker is well mixed after ultrasonic decomposition.Will
Mixed liquor is transferred in autoclave, and 5-25 h are reacted at 180-220 DEG C；CdS NiMoS helical structure complex lights are obtained to urge
Agent, product is washed and is dried in vacuo.
Novel composite nano light produces hydrogen auxiliary agent compound primary catalysts CdS nanorod shapeds into the light of CdS@NiMoS photochemical catalysts
H2-producing capacity is studied, and method is as follows：10-50 mg photochemical catalysts are weighed, are dispersed in 40-80 mL distilled water, Ran Houfen
Na is not added2SO3And Na2S under magnetic stirring, by the use of 300 W xenon lamps as visible light source, carries out light as photocatalysis sacrifice agent
Water decomposition production hydrogen experiment is reduced, reacting space same time carries out a test sample, and every kind of sample is carried out continuously 3-5 production hydrogen point
Analysis, carries out qualitative analysis with gas-chromatography, determines the content of product.Reaction reclaims catalyst after terminating.
The present invention is further detailed explanation with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The preparation and performance test of nano-photocatalyst CdS nanometer rods with Photocatalyzed Hydrogen Production performance.
（1）CdS presoma Cd (S2CNEt2)2Preparation：
Weigh a certain amount of Cd (NO3)2˙4H2O is dissolved in 50-80 mL water, weighs enough DDTCs（NaS2CNEt2·3H2O,
DDTC）It is dissolved in 40-50 mL water；Then the DDTC aqueous solution is slowly added dropwise to Cd (NO under magnetic stirring3)2The aqueous solution
In, magnetic agitation 5-20 min, by Vacuum filtration device, that is, obtain CdS presomas Cd (DDTC) at room temperature2, with distillation
Water and ethanol wash 3 times and are dried in vacuo 6-10 h respectively, you can it is stand-by to obtain white product；
（2）The preparation of CdS nanometer rods：
1.0-2.0 g Cd (DDTC) are added in autoclave2, 70-80 mL anhydrous ethylenediamines are then added thereto, will
It reacts 6-48 h at 120-200 DEG C, and product is centrifuged and washed respectively 3 times with distilled water and ethanol, is dried in vacuo 6-10
H, that is, obtain yellow CdS nanometer rods.
（3）Nano-photocatalyst CdS light H2-producing capacity research：
10-50 mg photochemical catalysts are weighed, is dispersed in 40-80 mL distilled water, is then respectively adding Na2SO3With
Na2S under magnetic stirring, by the use of 300 W xenon lamps as visible light source, carries out photo-reduction water decomposition as photocatalysis sacrifice agent
Hydrogen experiment is produced, reacting space same time carries out a test sample, and every kind of sample is carried out continuously 3-5 production hydrogen analysis, with gas phase color
Spectrum carries out qualitative analysis, determines the content of product.Reaction reclaims catalyst after terminating.
Embodiment 2
Nano-photocatalyst CdS@MoS with excellent Photocatalyzed Hydrogen Production performance2The preparation and performance test of helical structure.
80-150 mg CdS nanometer rods are added in the beaker containing 15-25 mL distilled water, and contain 15-25 another
Na is separately added into the beaker of mL distilled water2MoO4· 2H2O and enough CN2H4S；Reactant in beaker mixes after ultrasonic decomposition
Close uniform.Mixed liquor is transferred in 50 mL autoclaves, 5-25 h are reacted at 180-220 DEG C；Product is centrifuged and uses steaming
Distilled water and ethanol wash 3 times respectively, are dried in vacuo 6-10h, that is, obtain CdS MoS2Helical structure composite catalyst.Contrast a system
Arrange the reaction solution of different Mo/Cd amount ratios：0th, 5%, 10%, 15%, 20%, 25%, obtain the CdS@MoS of optimal Mo load capacity2Catalysis
The optimum amount ratio of agent, i.e. Mo/Cd is 15%.The platinum acid chloride solution of 2.5 mL concentration 5% is added in experiment, to its photocatalysis performance
Detected, and contrasted with the photocatalysis performance of the CdS nanometer rods of conventional load Pt auxiliary agents.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is same as Example 1.
Embodiment 3
The preparation and performance test of nano-photocatalyst CdS@NiMoS with excellent Photocatalyzed Hydrogen Production performance.
To the photochemical catalyst with optimal hydrogen manufacturing performance, i.e. Mo/Cd amount ratios are under 15% optimum load amount, to Ni from
Son doping is studied.80-150 mg CdS nanometer rods are added into the beaker containing 15-25 mL distilled water, and are contained to another
Have in the beaker of 15-25 mL distilled water and be separately added into Na2MoO4· 2H2O、Ni(NO3)2· 6H2O and enough CN2H4S；In beaker
Reactant after ultrasonic decomposition be well mixed.Mixed liquor is transferred in 50 mL autoclaves, reacts 5- at 180-220 DEG C
25 h；Product is centrifuged and washed respectively 3 times with distilled water and ethanol, 6-10 h is dried in vacuo, that is, obtains novel photocatalyst
CdS@NiMoS.Contrast a series of reaction solution of different Ni/Cd amount ratios：0th, 1%, 5%, 10%, 15%, obtain optimum N i load capacity
CdS@NiMoS catalyst, i.e., Ni optimum load amount be 1%.
In order to verify the stability of this catalyst, long-time hydrogen production reaction has been carried out, has observed its hydrogen-producing speed, and to reaction
Whether catalyst recovery afterwards carries out SEM and XRD and characterized, to compare the pattern of catalyst before and after light-catalyzed reaction and form steady
It is fixed.
In order to probe into the photocatalysis seawater H2-producing capacity of this catalyst, in Yellow Sea of China West Coast --- Tang Dao gulfs random quantity
A certain amount of seawater is taken, is directly used in photocatalysis hydrogen production reaction after settlement.The photochemical catalyst with optimal H2-producing capacity is chosen, than
Compared with its photolysis of seawater hydrogen manufacturing and the difference of photodissociation distillation aquatic products hydrogen.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is same as Example 1.
Embodiment 4
Photocatalyzed Hydrogen Production nano-photocatalyst CdS and photocatalysis auxiliary agent MoS2, NiMoS physical mixtures preparation and light urge
Change H2-producing capacity test.
To verify novel photocatalysis auxiliary agent MoS2With NiMoS hetero-junctions is formed after chemical load to CdS nanorod surfaces
Structure and photocatalysis performance can be promoted, this experiment has especially synthesized the single phase catalysis auxiliary agent MoS without the load of CdS nanometer rods2And
NiMoS.Above-mentioned single phase catalysis auxiliary agent and major catalyst CdS are subjected to physical mixed by optimal hydrogen manufacturing amount ratio, and probe into its light
It is catalyzed H2-producing capacity.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is same as Example 1.
Fig. 1 is embodiment 1-3 SEM photograph, wherein figure (A), (B) are pure phase CdS Nanorods Catalysts；Scheme (C), (D)
For CdS@MoS2Helical structure Nanorods Catalyst；Scheme (E), (F) is CdS@NiMoS novel nano rods.As seen from the figure, great Liang Na
The co-catalyst load of rice sheet is grown in CdS nanorod surfaces, forms the good heterojunction structure in interface.The structure can promote electricity
Son transmission, the photoetch for providing a large amount of reactivity sites, suppressing CdS, play an important roll to improving H2-producing capacity.
Fig. 2 is embodiment 2-3 TEM photos, wherein figure (A), (B) are CdS@MoS2Helical structure Nanorods Catalyst；
Scheme (C), (D) is CdS@NiMoS novel nano rod catalyst.Visible obvious nanometer laminated structure NiMoS lattice bar in figure
Line, illustrate that light production hydrogen auxiliary agent has successfully been loaded to major catalyst CdS nanorod surfaces.
Fig. 3 be embodiment 1-4 photocatalysis hydrogen production figure, wherein CdS@MoS2One is classified as different MoS2The CdS@of load capacity
MoS2, CdS and MoS2Physical mixture is compared with the CdS of supporting Pt hydrogen-producing speed.As seen from the figure, with physical mixed CdS with
MoS2And carried noble metal Pt is compared, CdS chemical loads MoS2Photocatalysis performance significantly improves afterwards；And MoS2During load capacity 15% this
Catalyst has optimal H2-producing capacity.CdS@NiMoS mono- are classified as the CdS@NiMoS and CdS and NiMoS of different NiMoS load capacity
Physical mixture hydrogen-producing speed compares.As seen from the figure, after loading Ni, the Photocatalyzed Hydrogen Production speed of catalyst significantly improves, when
This catalyst has optimal H2-producing capacity when NiMoS load capacity is 1%.
Fig. 4 is CdS@1%NiMoS photocatalysis distilled water-seawater hydrogen manufacturing figure of embodiment 3, it is known that the catalyst photolysis of seawater
Hydrogen manufacturing yield is suitable with the ability of photodissociation distilled water, illustrates that this catalyst is used for seawater hydrogen manufacturing and has great potential.
Fig. 5 is the long-time photocatalysis hydrogen production figure of embodiment 3, it is known that after long-time is reacted, catalyst still has
Good H2-producing capacity, illustrate that the catalyst stability is good.
Fig. 6-7 is the XRD and SEM photograph of embodiment 3, it is known that after long-time hydrogen manufacturing, CdS@1%NiMoS photochemical catalysts
Pattern and structure do not change substantially, it was demonstrated that the catalyst has good structure and stability.
The preparation method of the photochemical catalyst of the present invention realizes spiral compound nanometer photocatalyst by two step hydrothermal techniques
Synthesis, synthesized first in ethylenediamine system size uniform, pattern rule CdS nanometer rods, then pressurizeed by hydro-thermal
Make Na2MoO4、Ni(NO3)2Laminate sulfide NiMoS corresponding to thiocarbamide reaction synthesis, and form hetero-junctions with nano bar-shape CdS
Structure CdS@NiMoS.The catalyst shows excellent Photocatalyzed Hydrogen Production performance, and seawater hydrogen manufacturing yield is up to 19.147
mmol·g-1·h-1, new catalyst Research idea is provided for new energy development.
The above described is only a preferred embodiment of the present invention, being not the limitation for making other forms to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (2)
1. a kind of preparation method of photochemical catalyst by the addition agent modified formation of Photocatalyzed Hydrogen Production, the Photocatalyzed Hydrogen Production auxiliary agent are
Composite Nano stratiform, the photochemical catalyst are to be coated on one-dimensional rod-like CdS major catalyst tables by Photocatalyzed Hydrogen Production auxiliary agent NiMoS
The helical structure that face is formed, expression formula：CdS@NiMoS, it is characterised in that comprise the following steps：
（1）Utilize solvent structure major catalyst CdS nanometer rods；
（2）Utilize hydro-thermal method synthesis Photocatalyzed Hydrogen Production auxiliary agent and the compound catalyst CdS@NiMoS of major catalyst；
Specifically use following steps：
（1）CdS presoma Cd (S2CNEt2)2Preparation：By cadmium nitrate Cd (NO3)2·4H2O and DDTC press 1:2 mole score
It is not dissolved in suitable quantity of water, then the DDTC aqueous solution is slowly added dropwise to Cd (NO under magnetic stirring3)2In the aqueous solution, that is, obtain
CdS presoma Cd (S2CNEt2)2, product is washed and is dried in vacuo；
（2）The preparation of CdS nanometer rods：Ethylenediamine is added in autoclave to the 70-80% of its volume, then adds Cd thereto
(S2CNEt2)2, it is reacted into 6-48 h at 120-200 DEG C, that is, obtains CdS nanometer rods, product is washed and is dried in vacuo；
（3）It is prepared by photochemical catalyst CdS@NiMoS hydro-thermal method：80-150 is added in the beaker containing 15-25 mL distilled water
Mg CdS nanometer rods, and it is another containing the beaker of 15-25 mL distilled water in be separately added into Na2MoO4、Ni(NO3)2With it is enough
Thiocarbamide, control Photocatalyzed Hydrogen Production auxiliary agent NiMoS and CdS proportion are in 0.01-0.25:1；Reactant ultrasound point in beaker
It is well mixed after solution, mixed liquor is transferred in autoclave, 5-25 h is reacted at 180-220 DEG C；Helical structure is obtained to answer
Catalyst is closed, product is washed and is dried in vacuo.
2. pass through photocatalysis made from the preparation method of the photochemical catalyst of the addition agent modified formation of Photocatalyzed Hydrogen Production described in claim 1
Application of the agent in terms of photocatalysis natural sea aquatic products hydrogen.
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| CN113912652A (en) * | 2021-08-30 | 2022-01-11 | 淮北师范大学 | Photocatalytic hydrogen production catalyst and preparation method thereof |
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