阅读说明：本技术 一种用于光解水制氢的中空多级p-n结NiO@CdS复合纳米材料及其制备方法 (A kind of hollow multistage p-n junction NiO@CdS composite nano materials and preparation method thereof for photolysis water hydrogen ) 是由 邓崇海 叶凡 王韬 吴云 王黎丽 刘伶俐 杨蕾 董强 于 2019-09-05 设计创作，主要内容包括：本发明涉及一种用于光解水制氢的中空多级p-n结NiO@CdS复合纳米材料及其制备方法,NiO@CdS复合材料由n-CdS纳米颗粒紧密负载在p-NiO空心微球的表面上构成,CdS纳米颗粒的粒径为10-30nm,NiO空心微球的外直径为0.8-1.2μm,由多孔的厚度约8nm的NiO纳米片交叠组装而成。该方法采用廉价易得的镍源和镉源,通过四步工艺技术路线将n-CdS纳米颗粒负载在p-NiO空心微球的表面上,制得p-n结NiO/CdS复合纳米中空结构。此复合材料结构新颖,比表面积大,可促进光生载流子的有效分离,作为可见光催化剂具有优越的光解水制氢性能。(The hollow multistage p-n junction NiO@CdS composite nano materials and preparation method thereof that the present invention relates to a kind of for photolysis water hydrogen, NiO@CdS composite material is closely supported on the surface of p-NiO tiny balloon by n-CdS nano particle and is constituted, the partial size of CdS nano particle is 10-30nm, the overall diameter of NiO tiny balloon is 0.8-1.2 μm, is assembled by the NiO nanometer sheet of porous thickness about 8nm is overlapping.This method uses nickel source cheap and easy to get and cadmium source, and n-CdS nano particle is supported on the surface of p-NiO tiny balloon by four step process technology paths, and p-n junction NiO/CdS composite Nano hollow structure is made.This composite structure is novel, and large specific surface area can promote efficiently separating for photo-generated carrier, has superior photolysis water hydrogen performance as visible light catalyst.)

1. a kind of hollow multistage p-n junction [email protected] composite nano materials and preparation method thereof for photolysis water hydrogen, feature It is, is the spherical structure of inner hollow, spherical shell is assembled by each p-type nickel oxide nano piece, locating for nickel oxide nano piece The thickness direction of plane and spherical shell is consistent, and is enclosed between adjacent nanometer sheet and is constituted hole, the surface of nickel oxide nano piece For meso-hole structure, N-shaped cadmium sulfide nanoparticles are supported on the surface of p-type nickel oxide nano piece, form the NiO/ with p-n junction CdS composite nanostructure.

2. the hollow multistage p-n junction [email protected] composite nano materials according to claim 1 for photolysis water hydrogen, It being characterized in that, cadmium sulfide is hexagonal wurtzite phase structure, and the partial size of nano particle is 10-30nm, and nickel oxide is cube phase structure, The overall diameter of hollow microsphere is 0.8-1.2 μm, is assembled by the porous nanometer sheet with a thickness of 7~9nm is overlapping.

3. a kind of preparation method of the hollow multistage p-n junction [email protected] composite nano materials for photolysis water hydrogen, feature exist In, including preparation NiO-Cd (Tu)_x ²⁺Hollow microsphere and by NiO-Cd (Tu)_x ²⁺Hollow microsphere is heat-treated to obtain multistage p-n Tie [email protected] composite nano materials.

4. the system of the hollow multistage p-n junction [email protected] composite nano materials according to claim 3 for photolysis water hydrogen Preparation Method, which is characterized in that NiO-Cd (Tu)_x ²⁺The preparation method of hollow microsphere is specific as follows:

Solution A is mixed with solution B and carries out isothermal reaction, then carries out baking processing obtaining NiO to the product after isothermal reaction Hollow microsphere, then disperse NiO hollow microsphere in solution C, solution D progress reaction treatment is added, NiO-Cd (Tu) is made_x ²⁺In Empty microballoon；

Solution A is nickel source solution；

Solution B is precipitant solution；

Solution C is cadmium source solution；

Solution D is sulphur source solution.

5. the system of the hollow multistage p-n junction [email protected] composite nano materials according to claim 3 for photolysis water hydrogen Preparation Method, which is characterized in that be heat-treated as microwave treatment.

6. the system of the hollow multistage p-n junction [email protected] composite nano materials according to claim 4 for photolysis water hydrogen Preparation Method, which is characterized in that solution A is that nickel chloride solution is formed with ammonium hydroxide mixed preparing, and 4mL is added according to every 1mol nickel chloride Ammonium hydroxide ratio is configured, and the mass concentration of ammonium hydroxide is 25%-28%.

7. the system of the hollow multistage p-n junction [email protected] composite nano materials according to claim 4 for photolysis water hydrogen Preparation Method, which is characterized in that it is 1:1 that solution B, which is aqueous solution of urea, solution A and solution B according to the molar ratio of nickel chloride and urea, ~10 carry out hybrid reaction.

8. the system of the hollow multistage p-n junction [email protected] composite nano materials according to claim 4 for photolysis water hydrogen Preparation Method, which is characterized in that solution D be thiourea solution and ethylenediamine mixed liquor, according to every 1mol thiocarbamide be added 0.1~ The ratio of 0.4mL ethylenediamine is hybridly prepared into.

9. the system of the hollow multistage p-n junction [email protected] composite nano materials according to claim 4 for photolysis water hydrogen Preparation Method, which is characterized in that solution C is that cadmium acetate aqueous solution, solution C and solution D are according to the molar ratio of cadmium acetate and thiocarbamide 0.1~1:1 is reacted.

10. the hollow multistage p-n junction [email protected] composite nano materials according to claim 4 for photolysis water hydrogen Preparation method, which is characterized in that solution A is reacted with solution B to be carried out in thermostat water bath, and the temperature of water-bath is 90 DEG C, reaction Time is 2.5h, reaction product is filtered, is washed, is dried, grind after obtain Ni (OH)₂Hollow microsphere.

11. the hollow multistage p-n junction [email protected] composite nano materials according to claim 10 for photolysis water hydrogen Preparation method, which is characterized in that calcination process is by Ni (OH)₂Hollow microsphere is roasted to obtain NiO in Muffle furnace hollow Microballoon, control maturing temperature are 400 DEG C, and the time is 2 hours.

12. the hollow multistage p-n junction [email protected] composite nano materials according to claim 4 for photolysis water hydrogen Preparation method, which is characterized in that after NiO hollow microsphere is impregnated in solution C, ultrasonic disperse 10min is added solution D and mixes, adopts It is sealed with PE film, magnetic agitation reacts 12h, obtains the NiO-Cd (Tu) of Adsorption of Cadmium complex_x ²⁺Hollow microsphere.

13. the hollow multistage p-n junction [email protected] composite nano materials according to claim 5 for photolysis water hydrogen Preparation method, which is characterized in that microwave heating time 30min, power 800W.

Technical field

The present invention relates to visible light catalyst material preparation technical fields, and in particular to a kind of in photolysis water hydrogen Empty multistage p-n junction [email protected] composite nano materials and preparation method thereof.

Background technique

Since modern times, due to largely consuming the fossil feedstocks such as coal, petroleum and natural gas, facing mankind greatly Energy crisis and severe problem of environmental pollution.The research for finding new energy has been to be concerned by more and more people.Hydrogen Energy, its conduct Secondary energy sources, have cleaning, efficiently, safety, many advantages, such as can storing, can transporting, generally by it is believed that be it is a kind of most Free of contamination green energy resource of ideal new century, therefore receive the great attention of various countries.Solar energy is that the mankind are inexhaustible, is used The inexhaustible permanent energy, be circular economy using solar energy photocatalytic hydrogen production by water decomposition, the most effective approach of green hydrogen manufacturing One of.

Photolysis water hydrogen technology starts from 1972, first by two professors of Tokyo Univ Japan Fujishima A and Honda K Secondary report finds TiO₂Single Crystalline Electrodes photochemical catalyzing is to generate this phenomenon of hydrogen, to disclose straight using solar energy A possibility that connecing hydrogen production by water decomposition opens the research road using solar photolysis water hydrogen.As electrolysis water is to partly The differentiation of the multiphase photocatalysis of conductor photocatalytic hydrogen production by water decomposition and TiO₂The successive discovery of photochemical catalyst in addition, risen with The research of photocatalysis method hydrogen production by water decomposition (abbreviation photocatalytic water), and the synthesis of photochemical catalyst, in terms of obtain it is larger Progress.

The generally existing operation of photochemical catalyst that is more, but preparing is studied for the photochemical catalyst of hydrogen production by water decomposition at present The defects such as method is cumbersome, and photochemical catalyst catalytic efficiency is low, a kind of such as entitled " preparation of p-n junction hollow sphere and in photocatalysis point Application in solution water hydrogen manufacturing " (number of patent application: is recorded following skill in Chinese patent application file 200910023546.8) Art scheme: weighing suitable amount of sucrose and be configured to aqueous sucrose solution, be put into autoclave, and hydrothermal synthesis carbon is received at a temperature of 165 DEG C Rice ball, as hard mould agent；Weigh appropriate Cd (NO₃)₂·4H₂O is configured to aqueous solution；Weigh appropriate Na₂S·9H₂O is configured to water Solution；At room temperature, Nano carbon balls are dispersed in dehydrated alcohol, carry out ultrasonic wave dispersion, drying；By Cd (NO₃)₂·4H₂O Aqueous solution be impregnated in the Nano carbon balls of preparation, room temperature is dried, be made cadmium ion package Nano carbon balls C-Cd, in room temperature Under, by the Na in step 3)₂S·9H₂The aqueous solution of O is slowly added dropwise into prepared C-Cd, impregnates, and washs, and drying obtains The Nano carbon balls C-CdS of cadmium sulfide package, weighs suitable Ni (NO₃)₂·6H₂O is configured to aqueous solution；By Ni obtained (NO₃)₂6H2O aqueous solution, which is slowly added dropwise into the C-CdS of preparation, to be impregnated, and room temperature is dried, and the cadmium sulfide of nickel ion cladding is made Nano carbon balls C-CdS-Ni weighs appropriate NaOH and is configured to aqueous solution, and the cadmium sulfide carbon nanometer coated to nickel ion is slowly added dropwise In ball C-CdS-Ni, steeped overnight, washing and drying obtains and successively wraps up answering for cadmium sulfide and NiOH core-shell structure on carbon core Condensation material C-CdS-Ni (OH)₂；Again by prepared composite material of core-shell structure C-CdS-Ni (OH)₂, in 400 in Muffle furnace DEG C roasting 2h, obtain p-n junction hollow sphere NiO-CdS nanocomposite.

Although the above method has acquired p-n junction hollow sphere NiO-CdS nanocomposite, but need in preparation prefabricated Standby Nano carbon balls do hard template, and process is cumbersome, low output, and the hollow sphere NiO-CdS nanocomposite of preparation is not significant Micro nano structure feature, it is poor applied to photocatalytic water H2-producing capacity as visible light catalyst, it needs to be further improved.

Summary of the invention

The object of the present invention is to provide a kind of hollow multistage p-n junction [email protected] composite Nano materials for photolysis water hydrogen Material, yield is high, reproducible, and raw material is cheap and easy to get, is suitble to industrialization production, and realize the effective use and green of solar energy The clean manufacturing of the energy.

The technical solution that the present invention takes is specific as follows:

A kind of hollow multistage p-n junction [email protected] composite nano materials for photolysis water hydrogen, are the spherical junctions of inner hollow Structure, spherical shell are assembled by each p-type nickel oxide nano piece, and the thickness direction of plane locating for nickel oxide nano piece and spherical shell is kept Unanimously, it is enclosed between adjacent nanometer sheet and constitutes hole, the surface of nickel oxide nano piece is meso-hole structure, N-shaped cadmium sulfide nano Particulate load forms the NiO/CdS composite nanostructure with p-n junction on the surface of p-type nickel oxide nano piece.

Cadmium sulfide is hexagonal wurtzite phase structure, and the partial size of nano particle is 10-30nm, and nickel oxide is cube phase structure, The overall diameter of hollow microsphere is 0.8-1.2 μm, is assembled by the porous nanometer sheet with a thickness of 7~9nm is overlapping.

The present invention also provides a kind of systems of hollow multistage p-n junction [email protected] composite nano materials for photolysis water hydrogen Preparation Method, including preparation NiO-Cd (Tu)_x ²⁺Hollow microsphere and by NiO-Cd (Tu)_x ²⁺Hollow microsphere is heat-treated to obtain multistage P-n junction [email protected] composite nano materials.

NiO-Cd(Tu)_x ²⁺The preparation method of hollow microsphere is specific as follows:

Solution A is mixed with solution B and carries out isothermal reaction, then carries out baking processing obtaining NiO to the product after isothermal reaction Hollow microsphere, then disperse NiO hollow microsphere in solution C, solution D progress reaction treatment is added, NiO-Cd (Tu) is made_x ²⁺In Empty microballoon.

Solution A is nickel source solution；

Solution B is precipitant solution；

Solution C is cadmium source solution；

Solution D is sulphur source solution.

Heat treatment is microwave treatment.

Solution A is that nickel chloride solution is formed with ammonium hydroxide mixed preparing, and the mixing of 4mL ammonium hydroxide is added according to every 1mol nickel chloride and matches It makes, the mass concentration of ammonium hydroxide is 25%-28%.

Solution B is that aqueous solution of urea, solution A and solution B are mixed according to the molar ratio of nickel chloride and urea for 1:1~10 Close reaction.

Solution D is the mixed liquor of thiourea solution and ethylenediamine, and 0.1~0.4mL ethylenediamine is added according to every 1mol thiocarbamide Ratio be hybridly prepared into.

Solution C be cadmium acetate aqueous solution, solution C and solution D according to the molar ratio of cadmium acetate and thiocarbamide be 0.1~1:1 into Row reaction.

Solution A is reacted with solution B to be carried out in thermostat water bath, and the temperature of water-bath is 90 DEG C, reaction time 2.5h, right Reaction product filtered, washed, being dried, grind after obtain Ni (OH)₂Hollow microsphere.

Calcination process is by Ni (OH)₂Hollow microsphere is roasted to obtain NiO hollow microsphere, control roasting in Muffle furnace Temperature is 400 DEG C, and the time is 2 hours.

After NiO hollow microsphere is impregnated in solution C, ultrasonic disperse 10min is added solution D and mixed, sealed using PE film, Magnetic agitation reacts 12h, obtains the NiO-Cd (Tu) of Adsorption of Cadmium complex_x ²⁺Hollow microsphere.

Microwave heating time is 30min, power 800W.

The technical effect that the present invention obtains are as follows:

1) the hollow multistage p-n junction [email protected] composite nano materials prepared by the present invention for photolysis water hydrogen, are received by cubic phase Rice piece, which interlocks, is assembled into the table that middle part has the multilevel structure of cavity to be closely supported on p-NiO tiny balloon by n-CdS nano particle It is constituted on face, it is hexagonal wurtzite phase structure that the partial size of CdS nano particle, which is 10-30nm, and the overall diameter of NiO tiny balloon is 0.8-1.2 μm, by thickness about 8nm(7~9nm) NiO nanometer sheet overlapping assemble.This composite structure is novel, compares table Area is big, can promote efficiently separating for photo-generated carrier, has superior photolysis water hydrogen performance, energy as visible light catalyst Enough photolysis water hydrogen performances that superior performance is realized in the lower situation of CdS content.

2) preparation method of a kind of multistage p-n junction [email protected] hollow microsphere of the invention, process equipment is simple, operation letter Just, yield is high, reproducible, and raw material is cheap and easy to get, is suitble to industrialization production.

3) multistage p-n junction [email protected] composite nano materials made from are as solar visible light catalytic decomposition water hydrogen manufacturing Photochemical catalyst, p-n junction coupling can promote efficiently separating for photo-generated carrier, and photolysis water hydrogen production is greatly improved Rate, and hydrogen production process is environmentally protective, realizes the effective use of solar energy and the clean manufacturing of green energy resource.

Detailed description of the invention

Fig. 1 is the technology path for preparing multistage p-n junction [email protected] composite nano materials；

Fig. 2 is X-ray diffraction analysis (XRD) spectrogram of the multistage p-n junction [email protected] composite nano materials prepared in embodiment 1；

Fig. 3 is the low power field emission scanning electron microscope of multistage p-n junction [email protected] composite nano materials prepared by embodiment 1 (FE-SEM) photo；

Fig. 4 is the high power field emission scanning electron microscope of multistage p-n junction [email protected] composite nano materials prepared by embodiment 1 (FE-SEM) photo；

Fig. 5 is transmission electron microscope (TEM) photo of multistage p-n junction [email protected] composite nano materials prepared by embodiment 1.

Specific embodiment

In order to which objects and advantages of the present invention are more clearly understood, the present invention is carried out specifically with reference to embodiments It is bright.It should be appreciated that following text is only used to describe one or more of specific embodiments of the invention, not to the present invention The protection scope specifically requested carries out considered critical.

The present invention utilizes cheap nickel source and cadmium source, using chemical bath deposition method-roasting heat treating process-dipping absorption method- Four step process route of microwave heating method.In preparation method, the dosage of Nickel dichloride hexahydrate is 1mmol, ammonium hydroxide (w/w:25~ 28%) volume is 4mL, and the dosage of urea is 1~10mmol；The dosage of NiO hollow microsphere is 0.1g, Cadmium diacetate dihydrate Dosage is 0.1~1mmol, and the dosage of thiocarbamide is 1.0mmol, and the volume of ethylenediamine is 0.1~0.4mL.The technology path of preparation As shown in Figure 1.