CN104492460A - Metallic oxide/metal sulfide hollow nanospheres as well as preparation method and application thereof - Google Patents
Metallic oxide/metal sulfide hollow nanospheres as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a metallic oxide/metal sulfide core-shell heterojunction hollow nanosphere. The inner layer of the spherical shell is a metallic oxide polycrystalline layer; the outer layer of the spherical shell is a metal sulfide polycrystalline layer; a heterojunction is formed between the metallic oxide polycrystalline layer and the metal sulfide polycrystalline layer; the thickness of each layer is 10 nanometers or below; and the diameter of the hollow sphere is 100-600 nanometers. The preparation method comprises the following steps: utilizing a template adsorption method, performing stepped adsorption and subsequent hydrothermal sulfuration, thereby preparing the metallic oxide/metal sulfide core-shell heterojunction hollow nanosphere. The metallic oxide/metal sulfide core-shell heterojunction hollow nanosphere disclosed by the invention is regular in structure, the thickness of the spherical shell is controllable, the grain size of the metallic oxide and metal sulfide is 10nm or below, the crystal quality is high, and the specific surface area is larger than 200m<2>/g. The method disclosed by the invention is simple and low in cost, has extremely wide range on selection of types of metallic oxides and selection of metal sulfides and contributes to industrialized application.
Description
Technical field
The present invention relates to a kind of nucleocapsid hetero-junctions nano-hollow ball and preparation method thereof, particularly relate to a kind of metal oxide/metal sulfide nucleocapsid hetero-junctions nano-hollow ball and preparation method thereof.
Background technology
The crisis that facing mankind coal, oil equal energy source are increasingly exhausted, finds the attention that new alternative energy source has obtained various countries.Solar energy is inexhaustible, the nexhaustible energy, and scientists is also for being transformed into solar energy storable electric energy, chemical energy and effort.Photocatalytic hydrogen production by water decomposition is the preferred approach of solar energy chemical conversion, because Hydrogen Energy has the incomparable advantage of other energy such as clean, safe, efficient as secondary energy sources.Climate change, fuel cell technology and the environmental problem become increasingly conspicuous have promoted the generation of " hydrogen economy ", replace or partly replace the direction that existing energy supply will become mankind's effort with hydrogen.At present, fossil fuel hydrogen manufacturing is industrial main path, and the whole world has the hydrogen of more than 95% to be manufactured by fossil fuel.Although the existing technical maturity of fossil resource hydrogen manufacturing, production cost is also lower, but resource-constrained and non-renewable, while acquisition hydrogen, in air, discharge a large amount of GHG carbon dioxide, will the two fold problem of shortage of resources and environment deterioration be faced with fossil resource hydrogen manufacturing.In the long run, this does not meet the needs of sustainable development.Therefore, utilize regenerative resource hydrogen manufacturing from non-fossil fuel, comprise biological hydrogen production, solar energy photocatalytic decomposing hydrogen-production and renewable energy power generation water electrolysis hydrogen production, it is one of effective way solving national energy security and environmental problem, wherein utilize solar energy photocatalytic hydrogen production by water decomposition, cause the extensive attention of countries in the world in recent years.
In semi-conducting material photocatalysis system, the effective separation realizing photo-generate electron-hole be by photocatalytic applications in the energy and environmental problem must through approach.Common single compound photochemical catalyst is metal oxide or sulfide semiconductor material.As TiO
2, WO
3, ZnS, CdS etc.They have all had in photocatalysis field applies very widely.But they also have the imperfect part of intrinsic, single semi-conducting material is because internal flaw and intrinsic compound, make photo-generate electron-hole after generation, have the photo-generate electron-hole directly and surface pairings compound inner at semiconductor close to 90%, instead of with water and pollutant effect.Which results in the waste of most photo-generate electron-hole, greatly limit the utilization to solar energy.Therefore, impel being separated of light induced electron and hole, suppress its compound, thus improve quantum efficiency, to make full use of solar energy, the stability improving photochemical catalyst is the key problem of modern photocatalysis field.At present, there is the modification technology of several conventional semiconductor light-catalysts, mainly comprise the compound etc. of doped transition metal ions and semiconductor light-catalyst.Among this, first two is owing to using a lot of yttrium, so receive the restriction of cost and resource reserve.Due to the very low and aboundresources of general semiconductor catalyst cost, so composite photocatalyst material is as TiO
2/ ZnS, WO
3/ CdS, Bi
2o
3/ CdS etc. cause and pay close attention to widely.It is because composite generally can form hetero-junctions that composite photocatalyst material has excellent performance than single catalysis material.Hetero-junctions is composited by heteroepitaxial growth by two kinds of different semi-conducting materials usually, produces the built in field that electron hole can be impelled to be separated because it is inner, so promoting that photo-generate electron-hole is separated the physicochemical property with uniqueness.Because nanometer size effect makes the diffusion length of electron hole greatly reduce, so the heterojunction semiconductor of nanoscale has more significantly photoelectric properties advantage than corresponding bulk semiconductor hetero-junctions.Preparation and research Nano semiconductor heterojunction material, explore its application, be one of research frontier of international nano material in recent years, have very large challenge and important scientific meaning.
Summary of the invention
The object of this invention is to provide that a kind of preparation method is simple, the large and metal oxide/metal sulfide core-shell nano hetero-junctions hollow ball that photocatalysis performance is good and preparation method thereof of specific area.
Metal oxide of the present invention/metal sulfide nucleocapsid hetero-junctions nano-hollow ball, its diameter is 100-600nm, hollow ball spherical shell internal layer is metal oxide polycrystal layer, skin is metal sulfide polycrystal layer, hetero-junctions is formed between metal oxide polycrystal layer and metal sulfide polycrystal layer, the thickness of every layer is at below 10nm, and in every layer, crystallite dimension is at below 10nm.
In above-mentioned nano-hollow ball, metal oxide is selected from the oxide of Al, B, Bi, Ba, Ca, Co, Cr, Ce, Cu, La, Ni, Fe, Zn, Sn, Rh, W, Ta, Ti, V, Hf, Mn, Mo, In, Li, Ge, Se, Zr, Mg, Ga or Si; Described metal sulfide is selected from the sulfide of Bi, Ba, Co, Cr, Ce, Cu, La, Ni, Fe, Zn, Sn, W, Ta, Ti, V, Hf, Mn, Mo, In, Ge, Se, Zr, Mg, Ga or Cd.
Prepare the method for above-mentioned metal oxide/metal sulfide nucleocapsid hetero-junctions nano-hollow ball, comprise the steps:
1) metal oxide adsorption liquid is configured:
Metal oxide salt is dissolved in solvent, be made into the metal oxide salting liquid that concentration of metal ions is 0.01 ~ 10M, described slaine is selected from the acetate of Al, B, Bi, Ba, Ca, Co, Cr, Ce, Cu, La, Ni, Fe, Zn, Sn, Rh, W, Ta, Ti, V, Hf, Mn, In, Li, Ge, Se, Zr, Mg, Ga or Si, chlorate, nitrate, sulfate or ester salt, and described solvent is deionized water, ethanol, formamide or ethylene glycol;
2) adsorb: surface is had the carbon ball of carboxyl and hydroxyl, PS ball or SiO
2ball template immerses in the adsorbent solution of step 1), makes spherical template content be 1g/L ~ 100g/L, ultrasonic spherical template is fully disperseed, centrifugal or suction filtration after stirring and adsorbing 2 ~ 48h, in 40 ~ 100 DEG C of drying 2 ~ 48h, obtains the spherical template after absorption;
3) remove template: by step 2) in dried carbon ball or PS ball heat treatment 3 ~ 60h at 300 ~ 800 DEG C remove carbon ball template or PS ball template obtains metallic oxide hollow sphere; Or by step 2) in dried SiO
2ball is at 300 ~ 800 DEG C after heat treatment 3 ~ 60h, then at 20 ~ 100 DEG C, immerse concentration be keep 0.5 ~ 24h in the NaOH solution of 1 ~ 20M, removes SiO
2ball template obtains metallic oxide hollow sphere;
4) adsorbent is added: be the metallic oxide hollow sphere adding 20 ~ 50mg step 3) in the D/W of 0.1 ~ 0.5M in the concentration of every 30mL, ultrasonic make it disperse after put into water heating kettle, 3 ~ 4h is reacted at 160 ~ 180 DEG C, after cool to room temperature, centrifugal, cleaning and at 40 ~ 100 DEG C dry 2 ~ 48h, obtain the metallic oxide hollow sphere that surface has adsorbent;
5) sulfide metal adsorption liquid is configured: be dissolved in solvent by sulfide metal salt, be configured to the sulfide metal salting liquid that concentration of metal ions is 0.01 ~ 10M, described slaine is selected from the acetate of Bi, Ba, Co, Cr, Ce, Cu, La, Ni, Fe, Zn, Sn, W, Ta, Ti, V, Hf, Mn, In, Ge, Se, Zr, Mg, Ga or Cd, chlorate, nitrate, sulfate or ester salt, and described solvent is deionized water, ethanol, formamide or ethylene glycol;
6) adsorb: the metallic oxide hollow sphere surface of step 4) with adsorbent immerses in the adsorbent solution of step 5), metallic oxide hollow sphere content is made to be 0.5g/L ~ 100g/L, ultrasonicly it is made fully to disperse, centrifugal or suction filtration after stirring and adsorbing 2 ~ 48h, at 40 ~ 100 DEG C, dry 2 ~ 48h, obtains the sample after absorption;
7) remove adsorbent: by sample dried in step 6) heat treatment 3 ~ 8h at 400 ~ 500 DEG C, obtain metal oxide/metal oxide nucleocapsid hollow ball;
8) sulfuration: the metal oxide/metal oxide nucleocapsid hollow ball and the 0.5 ~ 2g thioacetamide that add 20 ~ 50mg step 7) in the deionized water of every 30mL, be stirred to mix and put into water heating kettle, 6 ~ 10h is reacted at 160 ~ 180 DEG C, after cool to room temperature, centrifugal, cleaning and at 40 ~ 100 DEG C dry 2 ~ 48h, obtain metal oxide/metal sulfide nucleocapsid hetero-junctions nano-hollow ball.
Above-mentioned metal oxide/metal sulfide nucleocapsid hetero-junctions nano-hollow ball, can be used for photocatalysis, gas catalysis and gas sensing.
In the present invention, described surface has the preparation method of the spherical template of carboxyl and hydroxyl can with reference to Sun, X.; Li, Y.,
angewandte Chemie International Edition 2004, 43(29), 3827-3831, Lou, X. W.; Archer, L. A.; Yang, Z.,
advanced Materials 2008, 20(21), 3987-4019 and Wang, D.; Hisatomi, T.; Takata, T.; Pan, C.; Katayama, M.; Kubota, J.; Domen, K.,
angewandte Chemie International Edition 2013, 52(43), 11252-11256.
The present invention utilizes rich surface to contain the spherical template of anionic group, by stirring and adsorbing metal ion in adsorbent solution, forms inner layer metal oxide hollow sphere after removing template; Add adsorbent by hydro-thermal method on metallic oxide hollow sphere surface, then put into adsorbent solution adsorbing metal ions, annealing forms metal oxide/metal oxide core-shell nano hollow ball after removing adsorbent; Again by adding thioacetamide as vulcanizing agent, being metal sulfide by outer field for hollow ball metal oxide vulcanization, obtaining metal oxide/metal sulfide nucleocapsid hetero-junctions nano-hollow ball.
Beneficial effect of the present invention is: metal oxide of the present invention/metal sulfide nucleocapsid hetero-junctions nano-hollow ball, spherical shell is by metal oxide and metal sulfide is two-layer closely forms, hetero-junctions is formed between metal oxide and metal sulfide, and the thickness of every layer is all below 10 nanometers, hollow ball diameter is 100 ~ 600 nanometers, and metal oxide layer and metal sulfide layer are polycrystalline, and crystallite dimension is all at below 10nm, crystalline quality is high, and specific area is greater than 200 m
2/ g.Method of the present invention is simple, cost is lower, achieve effective compound of metal oxide and metal sulfide two-layer core shell structure, by forming hetero-junctions between the two, avoid the compound in light induced electron and hole, be conducive to being separated of light induced electron and hole, thus improve the photocatalysis performance of material, be conducive to the application of industrialization.
Accompanying drawing explanation
Fig. 1 is titanium oxide (TiO
2)/bismuth sulfide (Bi
2s
3) the XRD diffraction picture of nucleocapsid hetero-junctions nano-hollow ball.
Fig. 2 is titanium oxide (TiO
2)/bismuth sulfide (Bi
2s
3) the SEM picture of nucleocapsid hetero-junctions nano-hollow ball.
Fig. 3 is titanium oxide (TiO
2)/bismuth sulfide (Bi
2s
3) N of nucleocapsid hetero-junctions nano-hollow ball
2adsorption-desorption curve.
Fig. 4 is titanium oxide (TiO
2)/bismuth sulfide (Bi
2s
3) the photocatalysis performance curve of core-shell nano hetero-junctions hollow ball.
Detailed description of the invention
Embodiment 1
Titanium oxide (TiO
2)/bismuth sulfide (Bi
2s
3) nucleocapsid hetero-junctions nano-hollow ball:
(1) 0.34g butyl titanate is put into 100mL ethanol and is dissolved, obtain titanium ion solution, then in this adsorbent solution, add the carbon ball template that 1g surface has carboxyl and hydroxyl, ultrasonic spherical template is fully disperseed, centrifugal after stirring and adsorbing 12h, dry 12h at 60 DEG C, obtains the spherical template after absorption;
(2) sample obtained in step (1) heat treatment 6h at 400 DEG C is removed carbon ball template and obtain titanium oxide hollow ball housing;
(3) the concentration above-mentioned titanium oxide hollow ball of 20mg being joined 30mL is in 0.5M D/W, ultrasonic make hollow ball disperse after put into water heating kettle, at 160 DEG C, react 3h, after cool to room temperature, centrifugal, cleaning and at 60 DEG C dry 12h;
(4) configuration concentration is the bismuth ion aqueous solution of 0.3M, sample obtained for step (3) is all placed in the above-mentioned bismuth ion aqueous solution of 40mL, ultrasonicly makes it fully disperse, suction filtration after stirring and adsorbing 6h, dry 7h at 60 DEG C, obtains the sample after absorption;
(5) by dried sample heat treatment 8h at 400 DEG C in step (4), remove adsorbent and obtain titanium oxide/bismuth oxide nucleocapsid hollow ball;
(6) by 20mg above-mentioned, titanium oxide/bismuth oxide nucleocapsid hollow ball joins in the deionized water of 30mL, add 0.5g thioacetamide again, being stirred to after mixing puts in the water heating kettle of 40mL, 10h is reacted at 160 DEG C, after cool to room temperature, centrifugal, cleaning and in 80 DEG C of dry 8h, obtain titanium oxide (TiO
2)/bismuth sulfide (Bi
2s
3) nucleocapsid hetero-junctions nano-hollow ball.
The TiO that this example is obtained
2/ Bi
2s
3xRD, SEM test result of nucleocapsid hetero-junctions nano-hollow ball respectively as shown in Figure 1, 2, clearly can show it for hollow ball-shape structure, and hollow ball diameter is 100 ~ 250 nanometers, hollow ball is made up of titanium oxide polycrystal layer and bismuth-sulfide polycrystalline layer, every layer thickness is at below 10nm, crystallite dimension is TiO at below 10nm, Fig. 3
2/ Bi
2s
3the N of nucleocapsid hetero-junctions nano-hollow ball
2from curve, adsorption-desorption curve, can find out that the specific area of this heterojunction structure hollow ball is greater than 200 m
2.g
-1.Fig. 4 is TiO
2/ Bi
2s
3the photocatalysis performance comparison diagram of nucleocapsid hetero-junctions nano-hollow ball, shows relative to pure TiO
2hollow ball and Bi
2s
3hollow ball, TiO
2/ Bi
2s
3nucleocapsid hetero-junctions nano-hollow ball has excellent photocatalysis performance.
Embodiment 2
Tungsten oxide (WO
3)/zinc sulphide (ZnS) nucleocapsid hetero-junctions nano-hollow ball:
(1) 0.4g tungsten chloride is placed in 60mL deionized water and dissolves, and obtains tungsten ion solution, in this adsorbent solution, then add the SiO that 0.7g surface has carboxyl and hydroxyl
2ball template, ultrasonicly makes spherical template fully disperse, centrifugal after stirring and adsorbing 8h, dry 8h at 70 DEG C, obtains the spherical template after absorption;
(2) by the sample that obtains in step (1) at 400 DEG C after heat treatment 6h, then at 80 DEG C, immerse concentration be keep 4h in the NaOH solution of 5M, removes SiO
2ball template obtains tungsten oxide hollow ball housing;
(3) the concentration above-mentioned tungsten oxide hollow ball of 30mg being joined 30mL is in 0. 4M D/W, ultrasonic make hollow ball disperse after put into water heating kettle, at 170 DEG C, react 4h, after cool to room temperature, centrifugal, cleaning and at 50 DEG C dry 8h;
(4) configuration concentration is the ethanolic solution of the zinc ion of 0.4M, the sample that step (3) is obtained is placed in the above-mentioned zinc ion ethanolic solution of 40mL, and the ultrasonic sample that makes fully disperses, suction filtration after stirring and adsorbing 7h, dry 8h at 70 DEG C, obtains the sample after absorption;
(5) by dried sample heat treatment 6h at 400 DEG C in step (4), remove adsorbent and obtain tungsten oxide/zinc oxide nucleocapsid hollow ball;
(6) by the above-mentioned tungsten oxide of 30mg/zinc oxide nucleocapsid hollow ball joins in the deionized water of 30mL, add 1g thioacetamide again, being stirred to after mixing puts in the water heating kettle of 40mL, 8h is reacted at 170 DEG C, after cool to room temperature, centrifugal, cleaning and in 90 DEG C of dry 9h, obtain tungsten oxide (WO
3)/zinc sulphide (ZnS) nucleocapsid hetero-junctions nano-hollow ball.The WO that this example is obtained
3/ ZnS core shell hetero-junctions nano-hollow bulb diameter is 200-600nm.
Embodiment 3
Bismuth oxide (Bi
2o
3)/cadmium sulfide (CdS) nucleocapsid hetero-junctions nano-hollow ball:
(1) 0.6g bismuth nitrate is placed in 80mL ethylene glycol and dissolves, obtain bismuth ion solution, then in this adsorbent solution, add the PS ball template that 0.9g surface has carboxyl and hydroxyl, ultrasonic spherical template is fully disperseed, centrifugal after stirring and adsorbing 48h, dry 2h at 100 DEG C, obtains the spherical template after absorption;
(2) sample obtained in step (1) heat treatment 60h at 300 DEG C is removed PS ball template and obtain bismuth oxide hollow ball housing;
(3) the above-mentioned bismuth oxide hollow ball of 30mg being joined 30mL concentration is in the D/W of 0.4M, ultrasonic make hollow ball disperse after put into water heating kettle, at 180 DEG C, react 3h, after cool to room temperature, centrifugal, cleaning and in 100 DEG C of dry 48h;
(4) configuration concentration is the ethylene glycol solution of the cadmium ion of 10M, the sample that step (3) is obtained is all placed in the above-mentioned cadmium ion ethylene glycol solution of 40mL, and the ultrasonic sample that makes fully disperses, suction filtration after stirring and adsorbing 2h, in 40 DEG C of dry 48h, obtain the sample after absorption;
(5) by dried sample heat treatment 3h at 500 DEG C in step (4), remove adsorbent and obtain bismuth oxide/cadmium oxide nucleocapsid hollow ball;
(6) by 25mg above-mentioned, bismuth oxide/cadmium oxide nucleocapsid hollow ball joins in the deionized water of 15mL, add 1g thioacetamide again, being stirred to after mixing puts in the water heating kettle of 40mL, 6h is reacted at 180 DEG C, after cool to room temperature, centrifugal, cleaning and in 100 DEG C of dry 2h, obtain bismuth oxide (Bi
2o
3)/cadmium sulfide (CdS) nucleocapsid hetero-junctions nano-hollow ball.The Bi that this example is obtained
2o
3/ CdS nucleocapsid hetero-junctions nano-hollow bulb diameter is 300-500nm.
Embodiment 4
Iron oxide (Fe
2o
3)/silver sulfide (Ag
2s) nucleocapsid hetero-junctions nano-hollow ball:
(1) 0.5g iron chloride is placed in 100mL formamide and dissolves, obtain ferric ion solutions, then in this adsorbent solution, add the carbon ball template that 10g surface has carboxyl and hydroxyl, ultrasonic spherical template is fully disperseed, centrifugal after stirring and adsorbing 2h, dry 48h at 40 DEG C, obtains the spherical template after absorption;
(2) sample obtained in step (1) heat treatment 3h at 800 DEG C is removed carbon ball template and obtain iron oxide hollow ball housing;
(3) the concentration above-mentioned iron oxide hollow ball of 1g being joined 600mL is in 0.1M D/W, ultrasonic make hollow ball disperse after put into water heating kettle, at 170 DEG C, react 4h, after cool to room temperature, centrifugal, cleaning and at 40 DEG C dry 2h;
(4) configuration concentration is the formamide solution of the silver ion of 0.01M, the sample that step (3) is obtained is all placed in the above-mentioned silver ion formamide solution of 10mL, and the ultrasonic sample that makes fully disperses, suction filtration after stirring and adsorbing 48h, dry 2h at 100 DEG C, obtains the sample after absorption;
(5) by dried sample heat treatment 5h at 400 DEG C in step (4), remove adsorbent and obtain iron oxide/silver oxide nucleocapsid hollow ball;
(6) by 50mg above-mentioned, iron oxide/silver oxide nucleocapsid hollow ball joins in the deionized water of 30mL, add 2g thioacetamide again, being stirred to after mixing puts in the water heating kettle of 40mL, 10h is reacted at 160 DEG C, after cool to room temperature, centrifugal, cleaning and in 100 DEG C of dry 2h, obtain iron oxide (Fe
2o
3)/silver sulfide (Ag
2s) nucleocapsid hetero-junctions nano-hollow ball.The Fe that this example is obtained
2o
3/ Ag
2s nucleocapsid hetero-junctions nano-hollow bulb diameter is 300-600nm.
Embodiment 5
Zinc oxide (ZnO)/copper sulfide (CuS) nucleocapsid hetero-junctions nano-hollow ball:
(1) 29g zinc nitrate is placed in 10mL ethanol and dissolves, obtain zinc ion solution, then in this adsorbent solution, add the carbon ball template that 0.01 g surface has carboxyl and hydroxyl, ultrasonic spherical template is fully disperseed, centrifugal after stirring and adsorbing 16h, dry 12h at 80 DEG C, obtains the spherical template after absorption;
(2) sample obtained in step (1) heat treatment 4h at 500 DEG C is removed carbon ball template and obtain zinc oxide hollow global shell;
(3) the concentration above-mentioned Zinc oxide hollow spheres of 10mg being joined 15mL is in 0. 4M D/W, ultrasonic make hollow ball disperse after put into water heating kettle, at 180 DEG C, react 3h, after cool to room temperature, centrifugal, cleaning and at 70 DEG C dry 18h;
(4) configuration concentration is the copper ion aqueous solution of 0.4M, the sample that step (3) is obtained is all placed in the above-mentioned copper ion aqueous solution of 20mL, and the ultrasonic sample that makes fully disperses, suction filtration after stirring and adsorbing 9h, in 50 DEG C of dry 18h, obtain the sample after absorption;
(5) by dried sample heat treatment 6h at 400 DEG C in step (4), remove adsorbent and obtain zinc oxide/cupric oxide nucleocapsid hollow ball;
(6) by 30mg above-mentioned, titanium oxide/cupric oxide nucleocapsid hollow ball joins in the deionized water of 30mL, add 1g thioacetamide again, being stirred to after mixing puts in the water heating kettle of 40mL, 6h is reacted at 180 DEG C, after cool to room temperature, centrifugal, cleaning and in 40 DEG C of dry 48h, obtain zinc oxide (ZnO)/copper sulfide (CuS) nucleocapsid hetero-junctions nano-hollow ball.ZnO/CuS nucleocapsid hetero-junctions nano-hollow bulb diameter that this example obtains is 100-600nm.
Embodiment 6
Nickel oxide (NiO)/molybdenum sulfide (MoS
2) nucleocapsid hetero-junctions nano-hollow ball:
(1) 0.9g nickel nitrate is placed in 100mL ethylene glycol and dissolves, and obtains nickel ion solution, in this adsorbent solution, then add the SiO that 1g surface has carboxyl and hydroxyl
2ball template, ultrasonicly makes spherical template fully disperse, centrifugal after stirring and adsorbing 12h, dry 10h at 70 DEG C, obtains the spherical template after absorption;
(2) by the sample that obtains in step (1) at 400 DEG C after heat treatment 6h, then at 100 DEG C, immerse concentration be keep 24h in the NaOH solution of 1M, removes SiO
2ball template obtains nickel oxide hollow ball housing;
(3) the concentration above-mentioned nickel oxide hollow ball of 40mg being joined 30mL is in 0.4M D/W, ultrasonic make hollow ball disperse after put into water heating kettle, at 170 DEG C, react 4h, after cool to room temperature, centrifugal, cleaning and at 80 DEG C dry 18h;
(4) configuration concentration is the molybdenum ion aqueous solution of 0.4M, the sample that step (3) is obtained is all placed in the above-mentioned molybdenum ion aqueous solution of 60mL, and the ultrasonic sample that makes fully disperses, suction filtration after stirring and adsorbing 8h, dry 18h at 80 DEG C, obtains the sample after absorption;
(5) by dried sample heat treatment 3h at 500 DEG C in step (4), remove adsorbent and obtain nickel oxide/molybdenum oxide nucleocapsid hollow ball;
(6) by the above-mentioned nickel oxide of 40mg/molybdenum oxide nucleocapsid hollow ball joins in the deionized water of 30mL, add 1.5g thioacetamide again, being stirred to after mixing puts in the water heating kettle of 40mL, 8h is reacted at 160 DEG C, after cool to room temperature, centrifugal, cleaning and in 80 DEG C of dry 12h, obtain nickel oxide (NiO)/molybdenum sulfide (MoS
2) nucleocapsid hetero-junctions nano-hollow ball.NiO/MoS that this example is obtained
2nucleocapsid hetero-junctions nano-hollow bulb diameter is 100-600nm.
Embodiment 7
Magnesia (MgO)/cobalt sulfide (CoS) core-shell nano hetero-junctions hollow ball:
(1) 2g magnesium nitrate is placed in 100mL deionized water and dissolves, and obtains magnesium ion solution, in this adsorbent solution, then add the SiO that 1g surface has carboxyl and hydroxyl
2ball template, ultrasonicly makes spherical template fully disperse, centrifugal after stirring and adsorbing 12h, dry 10h at 80 DEG C, obtains the spherical template after absorption;
(2) by the sample that obtains in step (1) at 400 DEG C after heat treatment 6h, then at 100 DEG C, immerse concentration be keep 24h in the NaOH solution of 1M, removes SiO
2ball template obtains nickel oxide hollow ball housing;
(3) the concentration above-mentioned magnesia hollow ball of 40mg being joined 30mL is in 0.2M D/W, ultrasonic make hollow ball disperse after put into water heating kettle, at 170 DEG C, react 4h, after cool to room temperature, centrifugal, cleaning and at 80 DEG C dry 18h;
(4) configuration concentration is the cobalt ions ethanolic solution of 0.4M, the sample that step (3) is obtained is all placed in the above-mentioned cobalt ions ethanolic solution of 60mL, and the ultrasonic sample that makes fully disperses, suction filtration after stirring and adsorbing 8h, dry 18h at 80 DEG C, obtains the sample after absorption;
(5) by dried sample heat treatment 3h at 500 DEG C in step (4), remove adsorbent and obtain magnesia/cobalt oxide nucleocapsid hollow ball;
(6) by the above-mentioned magnesia of 40mg/cobalt oxide nucleocapsid hollow ball joins in the deionized water of 30mL, add 1.5g thioacetamide again, being stirred to after mixing puts in the water heating kettle of 40mL, 8h is reacted at 160 DEG C, after cool to room temperature, centrifugal, cleaning and in 80 DEG C of dry 12h, obtain magnesia (MgO)/cobalt sulfide (CoS) nucleocapsid hetero-junctions nano-hollow ball.MgO/CoS nucleocapsid hetero-junctions nano-hollow bulb diameter that this example obtains is 100-600nm.
Claims (4)
1. metal oxide/metal sulfide nucleocapsid hetero-junctions nano-hollow ball, it is characterized in that described hollow ball diameter is 100-600nm, hollow ball spherical shell internal layer is metal oxide polycrystal layer, skin is metal sulfide polycrystal layer, hetero-junctions is formed between metal oxide polycrystal layer and metal sulfide polycrystal layer, the thickness of every layer is at below 10nm, and in every layer, crystallite dimension is at below 10nm.
2. metal oxide according to claim 1/metal sulfide nucleocapsid hetero-junctions nano-hollow ball, is characterized in that described metal oxide is selected from the oxide of Al, B, Bi, Ba, Ca, Co, Cr, Ce, Cu, La, Ni, Fe, Zn, Sn, Rh, W, Ta, Ti, V, Hf, Mn, Mo, In, Li, Ge, Se, Zr, Mg, Ga or Si; Described metal sulfide is selected from the sulfide of Bi, Ba, Co, Cr, Ce, Cu, La, Ni, Fe, Zn, Sn, W, Ta, Ti, V, Hf, Mn, Mo, In, Ge, Se, Zr, Mg, Ga or Cd.
3. prepare the method for metal oxide as claimed in claim 1/metal sulfide nucleocapsid hetero-junctions nano-hollow ball, it is characterized in that comprising the steps:
1) metal oxide adsorption liquid is configured:
Metal oxide salt is dissolved in solvent, be made into the metal oxide salting liquid that concentration of metal ions is 0.01 ~ 10M, described slaine is selected from the acetate of Al, B, Bi, Ba, Ca, Co, Cr, Ce, Cu, La, Ni, Fe, Zn, Sn, Rh, W, Ta, Ti, V, Hf, Mn, In, Li, Ge, Se, Zr, Mg, Ga or Si, chlorate, nitrate, sulfate or ester salt, and described solvent is deionized water, ethanol, formamide or ethylene glycol;
2) adsorb: surface is had the carbon ball of carboxyl and hydroxyl, PS ball or SiO
2ball template immerses in the adsorbent solution of step 1), makes spherical template content be 1g/L ~ 100g/L, ultrasonic spherical template is fully disperseed, centrifugal or suction filtration after stirring and adsorbing 2 ~ 48h, in 40 ~ 100 DEG C of drying 2 ~ 48h, obtains the spherical template after absorption;
3) remove template: by step 2) in dried carbon ball or PS ball heat treatment 3 ~ 60h at 300 ~ 800 DEG C remove carbon ball template or PS ball template obtains metallic oxide hollow sphere; Or by step 2) in dried SiO
2ball is at 300 ~ 800 DEG C after heat treatment 3 ~ 60h, then at 20 ~ 100 DEG C, immerse concentration be keep 0.5 ~ 24h in the NaOH solution of 1 ~ 20M, removes SiO
2ball template obtains metallic oxide hollow sphere;
4) adsorbent is added: be the metallic oxide hollow sphere adding 20 ~ 50mg step 3) in the D/W of 0.1 ~ 0.5M in the concentration of every 30mL, ultrasonic make it disperse after put into water heating kettle, 3 ~ 4h is reacted at 160 ~ 180 DEG C, after cool to room temperature, centrifugal, cleaning and at 40 ~ 100 DEG C dry 2 ~ 48h, obtain the metallic oxide hollow sphere that surface has adsorbent;
5) sulfide metal adsorption liquid is configured: be dissolved in solvent by sulfide metal salt, be configured to the sulfide metal salting liquid that concentration of metal ions is 0.01 ~ 10M, described slaine is selected from the acetate of Bi, Ba, Co, Cr, Ce, Cu, La, Ni, Fe, Zn, Sn, W, Ta, Ti, V, Hf, Mn, In, Ge, Se, Zr, Mg, Ga or Cd, chlorate, nitrate, sulfate or ester salt, and described solvent is deionized water, ethanol, formamide or ethylene glycol;
6) adsorb: the metallic oxide hollow sphere surface of step 4) with adsorbent immerses in the adsorbent solution of step 5), metallic oxide hollow sphere content is made to be 0.5g/L ~ 100g/L, ultrasonicly it is made fully to disperse, centrifugal or suction filtration after stirring and adsorbing 2 ~ 48h, at 40 ~ 100 DEG C, dry 2 ~ 48h, obtains the sample after absorption;
7) remove adsorbent: by sample dried in step 6) heat treatment 3 ~ 8h at 400 ~ 500 DEG C, obtain metal oxide/metal oxide nucleocapsid hollow ball;
8) sulfuration: the metal oxide/metal oxide nucleocapsid hollow ball and the 0.5 ~ 2g thioacetamide that add 20 ~ 50mg step 7) in the deionized water of every 30mL, be stirred to mix and put into water heating kettle, 6 ~ 10h is reacted at 160 ~ 180 DEG C, after cool to room temperature, centrifugal, cleaning and at 40 ~ 100 DEG C dry 2 ~ 48h, obtain metal oxide/metal sulfide nucleocapsid hetero-junctions nano-hollow ball.
4. a purposes for metal oxide as claimed in claim 1/metal sulfide nucleocapsid hetero-junctions nano-hollow ball, is characterized in that the application of this hollow ball in photocatalysis, gas catalysis and gas sensing.
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