CN104959153A - Auxiliary agent for photocatalytic production of hydrogen, and photocatalyst and preparation method and application thereof - Google Patents
Auxiliary agent for photocatalytic production of hydrogen, and photocatalyst and preparation method and application thereof Download PDFInfo
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- CN104959153A CN104959153A CN201510308310.4A CN201510308310A CN104959153A CN 104959153 A CN104959153 A CN 104959153A CN 201510308310 A CN201510308310 A CN 201510308310A CN 104959153 A CN104959153 A CN 104959153A
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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 invention provides a novel auxiliary agent for photocatalytic production of hydrogen. The auxiliary agent for photocatalytic production of hydrogen is nanometer layered NiMoS; and the photocatalyst with a NiMoS-coated CdS spiral structure is formed by modifying a one-dimensional rod-like CdS main catalyst with the nanometer layered NiMoS. The preparation method realizes synthesis of the spiral composite nanometer photocatalyst through two-step hydro-thermal technology and comprises the following steps: synthesizing a CdS nanorod with a uniform size and regular morphology in an ethene diamine system; and carrying out hydro-thermal pressurization to synthesize corresponding layered NiMoS through a reaction of Na2MoO4, Ni(NO3)2 and thiourea and allowing the layered NiMoS and the nanorod-like CdS to the heterostructure NiMoS-coated CdS. The photocatalyst shows excellent photocatalytic hydrogen production performance and enables seawater hydrogen production yield to reach 19.147 mmol/g/h; and a novel idea is provided for research and development of catalysts in the field of new energy development.
Description
Technical field
The invention belongs to catalysis material technical field, relate in particular to a kind of be applied to photocatalysis Decomposition distilled water and natural sea-water hydrogen manufacturing co-catalyst NiMoS and major catalyst CdS nanometer rods form spiral composite Nano metal sulfide photocatalyst and its preparation method and application.
Background technology
Photocatalysis solar energy is converted into can be significant by the fuel of human use.Hydrogen, as the widely used raw material of one, is play greatly effect in methyl alcohol and hydrocarbon at synthetic ammonia and carbon dioxide conversion.Natural sea-water is as a kind of inexhaustible natural resources simultaneously, and its development and utilization has huge prospect.Therefore the hydrogen manufacturing of semiconductor light-catalyst decomposing water with solar energy is utilized to cause extensive concern both domestic and external.
The visible light-responded catalyst that research allotment has appropriate band position is raising visible light catalytic hydrogen generation efficiency, promotes the research emphasis that photocatalysis technology further develops.
Summary of the invention
The invention provides the preparation method and application of a kind of new and effective Photocatalyzed Hydrogen Production auxiliary agent, photochemical catalyst and photochemical catalyst, not only significantly improve the hydrogen production efficiency utilizing sunshine, and seawater hydrogen manufacturing can be made full use of, significant to the development and utilization of new forms of energy.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
On the one hand, the invention provides a kind of novel photocatalysis and produce hydrogen auxiliary agent, this Photocatalyzed Hydrogen Production auxiliary agent is composite Nano stratiform, and chemical formula is NiMoS.
On the other hand, the invention provides a kind of photochemical catalyst being modified formation by Photocatalyzed Hydrogen Production auxiliary agent NiMoS, this photochemical catalyst is the helical structure being coated on the formation of one-dimensional rod-like CdS major catalyst surface by Photocatalyzed Hydrogen Production auxiliary agent NiMoS, chemical expression: CdS@NiMoS.The bar-shaped CdS major catalyst of NiMoS modification one-dimensional forms the helical structure of combining closely.
Laminar nano MoS
2have the two-dimensional structure of similar Graphene, be auxiliary agent excellent in photolysis water hydrogen reaction, its specific area is huge, can provide more reaction active site; Its band gap locations and band gap width mate with CdS nanometer rods, effectively can be compounded to form heterojunction structure; The a large amount of unsaturated sulphur atom of its layer structure marginal existence, significantly can improve the hydrogen manufacturing performance of catalyst.At MoS
2marginal position is introduced Ni ion and is regulated and controled, and forms NiMoS layer structure, improves Photocatalyzed Hydrogen Production efficiency further.
Again on the one hand, the invention provides a kind of preparation method of photochemical catalyst, comprise the following steps:
(1) solvent structure photocatalysis major catalyst CdS nanometer rods is utilized;
(2) the catalyst CdS@NiMoS of water heat transfer photocatalysis auxiliary agent and major catalyst compound is utilized.
Further, preparation process is specific as follows:
(1) CdS presoma Cd (S
2cNEt
2)
2preparation: by cadmium nitrate Cd (NO
3)
24H
2o and DDTC (NaS
2cNEt
23H
2o, NaDDTC) be dissolved in respectively in suitable quantity of water by the mol ratio of 1:2, then under magnetic stirring the DDTC aqueous solution is slowly dropped to Cd (NO
3)
2in the aqueous solution, namely obtain CdS presoma Cd (DDTC)
2, by product washing also vacuum drying;
(2) preparation of CdS nanometer rods: add the 70-80% of ethylenediamine to its volume in autoclave, then adds Cd (DDTC) wherein
2, it is reacted 6-48 h at 120-200 DEG C, namely obtains CdS nanometer rods, by product washing also vacuum drying;
(3) the hydro-thermal method preparation of CdS@NiMoS: add 80-150 mg CdS nanometer rods in the beaker containing 15-25 mL distilled water, and contain in the beaker of 15-25 mL distilled water at another and add Na respectively
2moO
4, Ni (NO
3)
2with enough thiocarbamides, control the proportion of auxiliary agent NiMoS and CdS at 0.01-0.25:1; Mix after reactant ultrasonic decomposition in beaker, mixed liquor is transferred in autoclave, at 180-220 DEG C, react 5-25 h; Namely CdS@NiMoS helical structure composite catalyst is obtained, by product washing also vacuum drying.
Wherein, the source of each element in auxiliary agent NiMoS is Ni (NO respectively
3)
2, Na
2moO
4and thiocarbamide,
The amount of substance of Ni, Mo is consistent with the amount of substance in final products, and thiocarbamide is sulphur source.
It is simple that preparation method of the present invention has technique, with low cost, reproducible feature, can prepare and form sunshine hydrogen production photocatalyst that is controlled, performance efficiency.
Above-mentioned photochemical catalyst and the application of Photocatalyzed Hydrogen Production auxiliary agent in photocatalysis hydrogen production.
Above-mentioned photochemical catalyst and the application of Photocatalyzed Hydrogen Production auxiliary agent in photocatalysis natural sea aquatic products hydrogen, can realize the development and utilization to marine resources.
Above-mentioned visible light catalytic auxiliary agent has good effect in simulated solar irradiation hydrogen manufacturing.It is the novel photocatalysis material meeting new forms of energy demand.This Photocatalyzed Hydrogen Production auxiliary agent can increase substantially the Photocatalyzed Hydrogen Production performance of major catalyst, and the expression formula of this addition agent modified major catalyst gained novel photocatalyst is CdS@NiMoS.
The light H2-producing capacity research of novel nano Photocatalyzed Hydrogen Production auxiliary agent NiMoS compound primary catalysts CdS nanometer rods of the present invention, method is as follows:
Take 10-50 mg photochemical catalyst, be dispersed in 40-80 mL distilled water, then add Na respectively
2sO
3and Na
2s as photocatalysis sacrifice agent, magnetic stir under, with 300 W xenon lamps as visible light source, carry out photo-reduction water decomposition and produce hydrogen experiment, reacting space same time carries out a test sample, and often kind of sample carries out 3-5 time continuously and produces hydrogen analysis, carry out qualitative analysis by gas-chromatography, determine the content of product.By catalyst recovery after reaction terminates.
Therefore, the present invention is based on hydro-thermal solvent-thermal method integrated reacting, by regulating kind and the additional proportion of different presoma, achieving the composition regulation and control that novel light produces hydrogen co-catalyst.The preparation of catalyst adopts the technology of hydro-thermal solvent-thermal method integration synthesis: first in ethylenediamine system, synthesized size uniform, the CdS nanometer rods of pattern rule, then makes Na by thermal and hydric environment
2moO
4, Ni (NO
3)
2laminate sulfide NiMoS corresponding to thiocarbamide Reactive Synthesis, and form heterojunction structure with nano bar-shape CdS.
Catalyst prepared by the present invention has stronger visible absorption, has increased substantially solar energy utilization ratio, shows very high Activity and stabill in simulated solar irradiation hydrogen manufacturing, and shows excellent properties in seawater hydrogen manufacturing.These features show that such catalyst has higher using value in new energy development field.
Described heterojunction structure composition metal sulfide photocatalyst is most preferred to be consisted of: the optimum load amount of Mo is 15%, is expressed as CdS@15%MoS
2; The optimum load amount of Ni is 1%, is expressed as CdS@1%NiMoS.Additive dosage in the composite photo-catalyst that said method obtains is verified as optimum proportioning, namely first on CdS nanorod foundations, finds MoS
2the best produce hydrogen load capacity; At optimization MoS
2on the basis of consumption, regulate the additional proportion of Ni ion to obtain the CdS@NiMoS composite photo-catalyst of optimal light catalyzing manufacturing of hydrogen effect.Above-mentioned catalyst combines the characteristic of different semiconductor, and the compound of various sulfide makes this composite catalyst have suitable position of energy band; Meanwhile, the unsaturated sulfide linkage at catalysis material edge and helical structure can provide a large amount of avtive spot, are conducive to hydrogen ion adsorption, are therefore the NEW TYPE OF COMPOSITE catalysis materials with excellent properties.
Compared with prior art, advantage of the present invention and good effect are: the present invention prepares helical structure novel photocatalysis by easy hydro-thermal reaction and produces hydrogen auxiliary agent composite nanoparticle, and be effectively applied to the hydrogen manufacturing of photodissociation distilled water and photolysis of seawater hydrogen manufacturing, particularly photolysis of seawater hydrogen manufacturing application prospect is extensive.
Accompanying drawing explanation
Fig. 1 is that novel photocatalysis prepared by embodiment 1-3 produces hydrogen auxiliary agent NiMoS modification CdS major catalyst gained CdS@NiMoS and traditional catalyst CdS and CdS@MoS
2scanning electron microscope sem photo comparison;
Fig. 2 is that novel photocatalysis prepared by embodiment 2-3 produces hydrogen auxiliary agent NiMoS modification CdS major catalyst gained CdS@NiMoS and traditional catalyst CdS@MoS
2transmission electron microscope TEM photo comparison;
Fig. 3 is that novel photocatalysis prepared by embodiment 1-4 produces hydrogen auxiliary agent NiMoS modification CdS major catalyst gained CdS@NiMoS and traditional catalyst CdS and CdS@MoS
2simulated solar irradiation hydrogen manufacturing productive rate comparison diagram;
Fig. 4 is that novel photocatalysis prepared by embodiment 3 produces the productive rate comparison diagram that hydrogen auxiliary agent NiMoS modifies CdS major catalyst gained CdS NiMoS difference photodissociation distilled water hydrogen manufacturing and photolysis of seawater hydrogen manufacturing;
Fig. 5 is that novel photocatalysis prepared by embodiment 3 produces the photocatalysis hydrogen production stability test figure that hydrogen auxiliary agent NiMoS modifies CdS major catalyst gained CdS@NiMoS;
Fig. 6 is that novel photocatalysis prepared by embodiment 3 produces the hydrogen auxiliary agent NiMoS modification CdS major catalyst gained CdS@NiMoS X-ray diffraction before and after Photocatalyzed Hydrogen Production (XRD) figure;
Fig. 7 is that novel photocatalysis prepared by embodiment 3 produces the SEM photo of hydrogen auxiliary agent NiMoS modification CdS major catalyst gained CdS@NiMoS before and after Photocatalyzed Hydrogen Production.
Detailed description of the invention
The present invention is directed to the deficiencies in the prior art, provide the preparation method of CdS@NiMoS sunshine hydrogen manufacturing nano-photocatalyst.
Visible ray of the present invention drives catalyst to be made up of, by hydro-thermal solvent-thermal method by this several semiconductors coupling co-catalyst (NiMoS) and major catalyst (CdS).
(1) CdS presoma Cd (S
2cNEt
2)
2preparation: by cadmium nitrate Cd (NO
3)
24H
2o and DDTC (NaS
2cNEt
23H
2o, DDTC) be dissolved in respectively in suitable quantity of water by the mol ratio of 1:2, then under magnetic stirring the DDTC aqueous solution is slowly dropped to Cd (NO
3)
2in the aqueous solution, namely obtain CdS presoma Cd (DDTC)
2, by product washing also vacuum drying;
(2) preparation of CdS nanometer rods: add the 70-80% of ethylenediamine to its volume in autoclave, then adds Cd (DDTC) wherein
2, it is reacted 6-48 h at 120-200 DEG C, namely obtains CdS nanometer rods, by product washing also vacuum drying;
(3) the hydro-thermal method preparation of CdS@NiMoS: add 80-150mgCdS nanometer rods in the beaker containing 15-25 mL distilled water, and contain in the beaker of 15-25 mL distilled water at another and add Na respectively
2moO
4, Ni (NO
3)
2with enough thiocarbamides, control the proportion of auxiliary agent NiMoS and CdS at 0.01-0.25:1; Reactant in beaker mixes after ultrasonic decomposition.Mixed liquor is transferred in autoclave, at 180-220 DEG C, react 5-25 h; Namely CdS@NiMoS helical structure composite photo-catalyst is obtained, by product washing also vacuum drying.
Novel composite nano light produces the light H2-producing capacity research that hydrogen auxiliary agent compound primary catalysts CdS nanometer rods forms CdS NiMoS photochemical catalyst, and method is as follows: take 10-50 mg photochemical catalyst, is dispersed in 40-80 mL distilled water, then adds Na respectively
2sO
3and Na
2s as photocatalysis sacrifice agent, magnetic stir under, with 300 W xenon lamps as visible light source, carry out photo-reduction water decomposition and produce hydrogen experiment, reacting space same time carries out a test sample, and often kind of sample carries out 3-5 time continuously and produces hydrogen analysis, carry out qualitative analysis by gas-chromatography, determine the content of product.By catalyst recovery after reaction terminates.
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Embodiment 1
There is the fabrication & properties test of the nano-photocatalyst CdS nanometer rods of Photocatalyzed Hydrogen Production performance.
(1) CdS presoma Cd (S
2cNEt
2)
2preparation:
Take a certain amount of Cd (NO
3)
2˙ 4H
2o is dissolved in 50-80 mL water, takes enough DDTC (NaS
2cNEt
23H
2o, DDTC) be dissolved in 40-50 mL water; Then under magnetic stirring the DDTC aqueous solution is slowly dropped to Cd (NO
3)
2in the aqueous solution, at room temperature magnetic agitation 5-20 min, through Vacuum filtration device, namely obtains CdS presoma Cd (DDTC)
2, wash respectively 3 times and vacuum drying 6-10 h with distilled water and ethanol, can white product be obtained stand-by;
(2) preparation of CdS nanometer rods:
1.0-2.0 g Cd (DDTC) is added in autoclave
2, then add 70-80 mL anhydrous ethylenediamine wherein, it is reacted 6-48 h at 120-200 DEG C, product is centrifugal and wash 3 times respectively with distilled water and ethanol, vacuum drying 6-10 h, namely obtain yellow CdS nanometer rods.
(3) the light H2-producing capacity research of nano-photocatalyst CdS:
Take 10-50 mg photochemical catalyst, be dispersed in 40-80 mL distilled water, then add Na respectively
2sO
3and Na
2s is as photocatalysis sacrifice agent, under magnetic stirring, with 300 W xenon lamps as visible light source, carry out photo-reduction water decomposition and produce hydrogen experiment, reacting space same time carries out a test sample, often kind of sample carries out 3-5 time continuously and produces hydrogen analysis, carries out qualitative analysis, determine the content of product by gas-chromatography.By catalyst recovery after reaction terminates.
Embodiment 2
There is the nano-photocatalyst CdS@MoS of excellent Photocatalyzed Hydrogen Production performance
2the fabrication & properties test of helical structure.
In the beaker containing 15-25 mL distilled water, add 80-150 mg CdS nanometer rods, and contain in the beaker of 15-25 mL distilled water at another and add Na respectively
2moO
42H
2o and enough CN
2h
4s; Reactant in beaker mixes after ultrasonic decomposition.Mixed liquor is transferred in 50 mL autoclaves, at 180-220 DEG C, react 5-25 h; Product is centrifugal and wash 3 times respectively with distilled water and ethanol, vacuum drying 6-10h, namely obtain CdS@MoS
2helical structure composite catalyst.Contrast the reactant liquor of a series of different Mo/Cd amount ratio: 0,5%, 10%, 15%, 20%, 25%, obtain the CdS@MoS of best Mo load capacity
2catalyst, namely the optimum amount ratio of Mo/Cd is 15%.Add the platinum acid chloride solution of 2.5 mL concentration 5% in experiment, its photocatalysis performance is detected, and contrast with the photocatalysis performance of the CdS nanometer rods of conventional load Pt auxiliary agent.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is identical with embodiment 1.
Embodiment 3
There is the fabrication & properties test of the nano-photocatalyst CdS@NiMoS of excellent Photocatalyzed Hydrogen Production performance.
To the photochemical catalyst with best hydrogen manufacturing performance, namely Mo/Cd amount ratio is under the optimum load amount of 15%, studies Ni ion doping.In the beaker containing 15-25 mL distilled water, add 80-150 mg CdS nanometer rods, and contain in the beaker of 15-25 mL distilled water to another and add Na respectively
2moO
42H
2o, Ni (NO
3)
26H
2o and enough CN
2h
4s; Reactant in beaker mixes after ultrasonic decomposition.Mixed liquor is transferred in 50 mL autoclaves, at 180-220 DEG C, react 5-25 h; Product is centrifugal and wash 3 times respectively with distilled water and ethanol, vacuum drying 6-10 h, namely obtain novel photocatalyst CdS@NiMoS.Contrast the reactant liquor of a series of different Ni/Cd amount ratio: 0,1%, 5%, 10%, 15%, obtain the CdS@NiMoS catalyst of optimum N i load capacity, namely the optimum load amount of Ni is 1%.
In order to verify the stability of this catalyst, carrying out long-time hydrogen production reaction, having observed its hydrogen-producing speed, and SEM and XRD sign has been carried out to reacted catalyst recovery, whether stablized with the pattern and composition that compare catalyst before and after light-catalyzed reaction.
In order to probe into the photocatalysis seawater H2-producing capacity of this catalyst, in Yellow Sea of China West Coast---the random measured amounts seawater in Tang Dao gulf, is directly used in photocatalysis hydrogen production reaction after sedimentation.Choose the photochemical catalyst with best H2-producing capacity, compare the difference that aquatic products hydrogen is distilled in its photolysis of seawater hydrogen manufacturing and photodissociation.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is identical with embodiment 1.
Embodiment 4
Photocatalyzed Hydrogen Production nano-photocatalyst CdS and photocatalysis auxiliary agent MoS
2, the preparation of NiMoS physical mixture and Photocatalyzed Hydrogen Production performance test.
For checking novel photocatalysis auxiliary agent MoS
2after chemical load to CdS nanorod surfaces, form heterojunction structure with NiMoS and can promote photocatalysis performance, the single phase catalysis auxiliary agent MoS without the load of CdS nanometer rods has been synthesized in this experiment especially
2and NiMoS.By best hydrogen manufacturing amount ratio, above-mentioned single phase catalysis auxiliary agent and major catalyst CdS are carried out physical mixed, and probe into its Photocatalyzed Hydrogen Production performance.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is identical with embodiment 1.
Fig. 1 is the SEM photo of embodiment 1-3, and wherein figure (A), (B) are pure phase CdS Nanorods Catalyst; Figure (C), (D) are CdS@MoS
2helical structure Nanorods Catalyst; Figure (E), (F) are CdS@NiMoS novel nano rod.As seen from the figure, a large amount of nano-sheet co-catalyst load growth, in CdS nanorod surfaces, forms the heterojunction structure that interface is good.The photoetch that this structure can promote electric transmission, provide a large amount of reactivity site, suppresses CdS, has important function to raising H2-producing capacity.
Fig. 2 is the TEM photo of embodiment 2-3, and wherein figure (A), (B) are CdS@MoS
2helical structure Nanorods Catalyst; Figure (C), (D) are CdS@NiMoS novel nano rod catalyst.The lattice fringe of visible significantly nanometer laminated structure NiMoS in figure, illustrates that light produces hydrogen auxiliary agent and is successfully loaded to major catalyst CdS nanorod surfaces.
Fig. 3 is the photocatalysis hydrogen production figure of embodiment 1-4, wherein CdS@MoS
2one is classified as different Mo S
2the CdS@MoS of load capacity
2, CdS and MoS
2physical mixture compares with the hydrogen-producing speed of the CdS of supporting Pt.As seen from the figure, with physical mixed CdS and MoS
2and carried noble metal Pt compares, CdS chemical load MoS
2rear photocatalysis performance significantly improves; And MoS
2during load capacity 15%, this catalyst has best H2-producing capacity.CdS@NiMoS and CdS and the NiMoS physical mixture hydrogen-producing speed that CdS@NiMoS mono-is classified as different Ni MoS load capacity compares.As seen from the figure, after load Ni, the Photocatalyzed Hydrogen Production speed of catalyst significantly improves, and when NiMoS load capacity is 1%, this catalyst has best H2-producing capacity.
Fig. 4 is the CdS@1%NiMoS photocatalysis distilled water-seawater hydrogen manufacturing figure of embodiment 3, and the ability of this catalyst photolysis of seawater hydrogen manufacturing productive rate known and photodissociation distilled water is suitable, illustrates that this catalyst has great potential for seawater hydrogen manufacturing.
Fig. 5 is the long-time photocatalysis hydrogen production figure of embodiment 3, and known after reaction for a long time, catalyst still has good H2-producing capacity, illustrates that this catalyst stability is good.
Fig. 6-7 is XRD figure and the SEM photo of embodiment 3, and known after long-time hydrogen manufacturing, pattern and the structure of CdS@1%NiMoS photochemical catalyst do not change substantially, confirm that this catalyst has good structure and stability.
The preparation method of photochemical catalyst of the present invention achieves the synthesis of spiral compound nanometer photocatalyst by two step hydrothermal techniques, in ethylenediamine system, first synthesized the CdS nanometer rods of size uniform, pattern rule, then makes Na by hydro-thermal pressurization
2moO
4, Ni (NO
3)
2laminate sulfide NiMoS corresponding to thiocarbamide Reactive Synthesis, and form heterojunction structure CdS NiMoS with nano bar-shape CdS.This catalyst shows excellent Photocatalyzed Hydrogen Production performance, and seawater hydrogen manufacturing productive rate can reach 19.147 mmolg
-1h
-1, for new energy development provides new catalyst Research idea.
The above is only preferred embodiment of the present invention, and be not restriction the present invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (8)
1. a Photocatalyzed Hydrogen Production auxiliary agent, is characterized in that: this Photocatalyzed Hydrogen Production auxiliary agent is composite Nano stratiform, and chemical formula is NiMoS.
2. by a photochemical catalyst for the addition agent modified formation of Photocatalyzed Hydrogen Production, it is characterized in that: this photochemical catalyst is the helical structure being coated on the formation of one-dimensional rod-like CdS major catalyst surface by Photocatalyzed Hydrogen Production auxiliary agent NiMoS, chemical expression: CdS NiMoS.
3. a preparation method for photochemical catalyst described in claim 2, is characterized in that comprising the following steps:
(1) solvent structure photocatalysis major catalyst CdS nanometer rods is utilized;
(2) the catalyst CdS@NiMoS of water heat transfer photocatalysis auxiliary agent and major catalyst compound is utilized.
4. the preparation method of photochemical catalyst according to claim 3, is characterized in that specifically adopting following steps:
(1) CdS presoma Cd (S
2cNEt
2)
2preparation: by cadmium nitrate Cd (NO
3)
24H
2o and DDTC are dissolved in suitable quantity of water respectively by the mol ratio of 1:2, then under magnetic stirring the DDTC aqueous solution are slowly dropped to Cd (NO
3)
2in the aqueous solution, namely obtain CdS presoma Cd (DDTC)
2, by product washing also vacuum drying;
(2) preparation of CdS nanometer rods: add the 70-80% of ethylenediamine to its volume in autoclave, then adds Cd (DDTC) wherein
2, it is reacted 6-48 h at 120-200 DEG C, namely obtains CdS nanometer rods, by product washing also vacuum drying;
(3) the hydro-thermal method preparation of CdS@NiMoS: add 80-150 mg CdS nanometer rods in the beaker containing 15-25 mL distilled water, and contain in the beaker of 15-25 mL distilled water at another and add Na respectively
2moO
4, Ni (NO
3)
2with enough thiocarbamides, control the proportion of auxiliary agent NiMoS and CdS at 0.01-0.25:1; Mix after reactant ultrasonic decomposition in beaker, mixed liquor is transferred in autoclave, at 180-220 DEG C, react 5-25 h; Namely CdS@NiMoS helical structure composite catalyst is obtained, by product washing also vacuum drying.
5. the application of Photocatalyzed Hydrogen Production auxiliary agent in photocatalysis hydrogen production described in claim 1.
6. the application of Photocatalyzed Hydrogen Production auxiliary agent described in claim 1 in photocatalysis natural sea aquatic products hydrogen.
7. the application of photochemical catalyst described in claim 2 in photocatalysis hydrogen production.
8. the application of photochemical catalyst described in claim 2 in 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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| CN115318307A (en) * | 2022-08-29 | 2022-11-11 | 四川启睿克科技有限公司 | Method for designing high-performance hydrogen production cocatalyst by introducing galvanic couple layer and constructing snowflake-shaped CuNi @ EDL/CdS catalyst |
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