CN102641741A - Composite photocatalyst with metal cadmium as core and heterostructure as shell and preparation method - Google Patents
Composite photocatalyst with metal cadmium as core and heterostructure as shell and preparation method Download PDFInfo
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- CN102641741A CN102641741A CN201110039337XA CN201110039337A CN102641741A CN 102641741 A CN102641741 A CN 102641741A CN 201110039337X A CN201110039337X A CN 201110039337XA CN 201110039337 A CN201110039337 A CN 201110039337A CN 102641741 A CN102641741 A CN 102641741A
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- cadmium
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- zinc oxide
- sulfide
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 title abstract description 9
- 239000002184 metal Substances 0.000 title abstract description 9
- 229910052793 cadmium Inorganic materials 0.000 title abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 56
- 239000011787 zinc oxide Substances 0.000 claims abstract description 44
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 13
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 238000013019 agitation Methods 0.000 claims description 17
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 15
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- UMJICYDOGPFMOB-UHFFFAOYSA-N zinc;cadmium(2+);oxygen(2-) Chemical compound [O-2].[O-2].[Zn+2].[Cd+2] UMJICYDOGPFMOB-UHFFFAOYSA-N 0.000 description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MQNRINNMYJOTSP-UHFFFAOYSA-N [O-2].[Zn+2].[S-2].[Cd+2] Chemical compound [O-2].[Zn+2].[S-2].[Cd+2] MQNRINNMYJOTSP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910007605 Zn—ZnO Inorganic materials 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- WSUTUEIGSOWBJO-UHFFFAOYSA-N dizinc oxygen(2-) Chemical compound [O-2].[O-2].[Zn+2].[Zn+2] WSUTUEIGSOWBJO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000280 vitalizing effect Effects 0.000 description 1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention relates to the field of photocatalysts, particularly relates to a composite high-efficient catalyst for hydrogen production by photocatalytic decomposition of water, wherein the catalyst adopts metal cadmium as a core and a heterostructure of zinc oxide and cadmium sulfide as a shell, and also relates to a preparation method; the invention solves the problem of effective and rapid transfer of zinc oxide and cadmium sulfide carriers in common composite catalysts, and greatly improves the catalytic efficiency. Zinc powder is used as a precursor; through the process of cadmium ion replacement reactions and sulfuration for cadmium sulfide shell generation, the high-efficient catalyst for hydrogen production by photocatalytic decomposition of water is obtained, which adopts metal cadmium as a core and a semiconductor heterostructure of zinc oxide and cadmium sulfide as a shell. In the catalyst, the molar ratio of metal cadmium is 50%-90%; the molar ratio of zinc oxide is 5%; and the molar ratio of cadmium sulfide is 5%-45%. The metal-core catalyst has high capability of hydrogen production by photocatalytic decomposition of water, has a hydrogen production rate of up to 23 mol h-1 g-1, and is expected to be used in the field of hydrogen production by water decomposition by solar energy.
Description
Technical field
The present invention relates to the photochemical catalyst field, being specially a kind of is nuclear with the cadmium metal, and zinc oxide and cadmium sulfide heterojunction structure are the composite efficient photocatalytic hydrogen production by water decomposition catalyst and the preparation method of shell.
Background technology
A large amount of uses of fossil energy bring serious environmental to pollute on the one hand, and particularly the carbon dioxide of carbon containing energy burning back generation makes global temperature raise, and fossil energy is limited on the other hand, along with the mankind exploit in a large number, just progressively move towards exhausted.Be badly in need of to seek a kind of energy capable of circulation of cleaning, hydrogen is as being a kind of clean energy resource carrier capable of circulation and widely paying attention to.But prepare a large amount of cleaning hydrogen, just can not obtain through using fossil to transform.Utilize photocatalysis method with solar energy under the effect of photochemical catalyst, it is that a kind of ideal then effectively prepares the hydrogen approach that water decomposition is produced hydrogen.The photocatalytic hydrogen production by water decomposition process is exactly to utilize sunshine vitalizing semiconductor catalyst to produce electronics and the hole with redox ability, splits water into hydrogen and oxygen.Usually for improve hydrogen-producing speed with make end product have only hydrogen, can add catch oxygen ion as sacrifice agent.
In the photocatalysis hydrogen production process research process, crucial problem is exactly the photochemical catalyst that how to design with synthesizing efficient.At present; Mostly a large amount of existing photochemical catalysts are single-phase photochemical catalyst, and efficient is lower, and polynary plyability catalyst not only helps the light abstraction width of extension system; More important electronics and the transfer in hole that can improve after photocatalysis excites, thus make catalysis system have higher catalytic activity.And in composite catalyst, it is most important that the transfer between heterogeneous semiconductor of electronics and hole becomes.Metal core can effectively improve the transfer of electron hole in the composite catalyst.Zinc oxide and cadmium sulfide are a kind of catalyst of the compound photocatalytic hydrogen production by water decomposition that shifts based on direct Z mechanism electronics; And not efficient as the transfer of photoexcitation carrier between the zinc oxide and the cadmium sulfide that influences the hydrogen production efficiency performance-critical, therefore need a kind of and cadmium metal of design for nuclear with the polynary composite photo-catalyst of the new type structure of hud of transfer fast of carrier between strengthening.
Summary of the invention
It is that nuclear zinc oxide and cadmium sulfide heterojunction structure are the catalyst and the preparation method of the composite efficient photocatalytic hydrogen production by water decomposition of shell with the cadmium metal that the object of the invention has been to provide a kind of; Solve the problem that common composite catalyst zinc oxide and cadmium sulfide carrier can not shift effectively fast, made catalytic efficiency significantly improve.
Technical scheme of the present invention is:
A kind of is the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure; Cadmium metal is nuclear; Semiconductor heterostructure zinc oxide and cadmium sulfide are shell; The shared molar ratio of cadmium metal is 50%～90% (being preferably 60%～85%), and the shared molar ratio of zinc oxide is 5%, and the shared molar ratio of cadmium sulfide is 5%～45% (being preferably 10%～35%).
Among the present invention, semiconductor heterostructure zinc oxide and cadmium sulfide are shell, are meant that the surface inlaying the shell of Zinc oxide particles for cadmium sulfide, and the thickness of cadmium sulfide shell is 5-50nm, and the Zinc oxide particles size is 3-50nm.
The invention provides a kind of is that nuclear zinc oxide and cadmium sulfide heterojunction structure are the composite efficient photocatalytic hydrogen production by water decomposition Preparation of catalysts method of shell with the cadmium metal.At first will contain the cadmium ion presoma and be dissolved in the deionized water, add then zinc powder ultrasonic with the magnetic agitation condition under, cadmium ion displacement metallic zinc.Add sulphurizing salt aqueous solution vulcanizing treatment, or the oven dry back uses the hydrogen sulfide gas vulcanizing treatment, obtain product for being that nuclear, zinc oxide and cadmium sulfide are the composite photocatalyst of shell with the cadmium metal.Wherein concrete being characterised in that:
1, contain a kind of that the cadmium ion presoma can be for caddy, cadmium nitrate, cadmium acetate, the concentration range of its aqueous solution is 0.03～0.5mol L
-1
2, the zinc particle that is adopted is of a size of 5～200 μ m.
3, the ultrasonic time of cadmium ion substituted metal zinc is 10min～1h, and the magnetic agitation time is 10min～2h.
4, the sulphurizing salt that adopts can be for vulcanized sodium or potassium sulfide a kind of, the concentration of its aqueous solution is 0.1～2mol L
-1, curing time is 0.5～48h, sulfuration after washing number of times 2～5 times, and the product bake out temperature is 50～120 ℃.
5, adopt hydrogen sulfide: the hydrogen sulfide gas flow is 5～100mL min
-1Curing temperature is 25～300 ℃.
6, products therefrom is made up of cadmium metal nuclear and zinc oxide and cadmium sulfide shell, and its molar ratio is between 50: 5: 45 to 90: 5: 5; Particle is mainly bar-shaped, diameter 100nm～2 μ m, length 300nm～20 μ m.
The present invention replaces zinc through cadmium ion and at first forms cadmium-zinc oxide, and has obtained cadmium metal nuclear zinc oxide cadmium sulfide shell composite catalyst through sulfuration at cadmium metal superficial growth cadmium sulfide shell.This catalyst has shown very high hydrogen-producing speed in simulated solar photocatalysis Decomposition water hydrogen manufacturing test, under the irradiation of natural daylight, show very high yield hydrogen performance equally.Catalyst cadmium-zinc & cadmium sulfide is introduced the core of cadmium metal as compound system through the method that ion replaces, the growth of original position cadmium sulfide is changed; Solve the problem that common composite catalyst zinc oxide and cadmium sulfide carrier can not shift effectively fast, made catalytic efficiency significantly improve.Thereby this composite photocatalyst is expected to be widely used in the photocatalytic hydrogen production by water decomposition field.
Advantage of the present invention and beneficial effect are:
1, the present invention is presoma with the zinc powder; Behind cadmium ion displacement zinc, sulfuration generates cadmium sulfide shell process, and having obtained with the cadmium metal is nuclear; Semiconductor heterostructure zinc oxide and cadmium sulfide are the high efficiency photocatalysis hydrogen production by water decomposition catalyst of shell, and maintenance has fine the contact with original zinc oxide.
2, cadmium sulfide is to form in the sulfuration of the surface in situ of cadmium in the inventive method, so cadmium sulfide is examined with cadmium combine well power is arranged.
3, the inventive method is introduced zinc oxide cadmium sulfide composite photocatalyst with cadmium metal nuclear, and the carrier that excites that illumination generates can be examined quick exchange through cadmium metal, thereby strengthens the cooperative effect between the composite catalyzing.
4, the thickness of the cadmium sulfide shell of the inventive method can be controlled through cure time, thereby arrives more excellent catalytic performance.
5, the inventive method is at room temperature synthesized this composite catalyst under the condition, can energy savings.
Description of drawings
Fig. 1. have the zinc powder (a) of zinc oxide shell and amplify SEM photo, the cadmium-zinc oxide (c) after the growth of cadmium ion displacement zinc of (b) and amplify the SEM photo of (d) and with the cadmium-zinc oxide after the sodium sulfide solution sulfuration and cadmium sulfide and amplification SEM photo; The insertion picture of c and e is its corresponding EDS collection of illustrative plates.
Fig. 2. the forming process sketch map of cadmium-zinc oxide and cadmium sulfide.
Fig. 3. zinc-zinc oxide and cadmium sulfide macroscopic view (a) and the local TEM photo that amplifies (b); Cadmium-zinc oxide and cadmium sulfide edge high-resolution photo (c) and amplification picture (d).
Fig. 4. the zinc powder of surface oxidation (a), the cadmium-zinc oxide (b) after replacing with cadmium and the ultraviolet-visible absorption spectroscopy of cadmium-zinc oxide after the vulcanizing treatment and cadmium sulfide (c).
Fig. 5. cadmium-zinc oxide after the sulfuration and the XRD figure of cadmium sulfide spectrum.
The collection of illustrative plates of the TEM photo (a) of the cadmium-zinc oxide of Fig. 6 .Pt load and cadmium sulfide and the EDX of diverse location (b:1 position, c:2 position, d:3 position).
The specific embodiment
Specify the present invention below in conjunction with embodiment.
Embodiment 1
At first, the 0.5g caddy is dissolved in the 20mL water, adds the zinc powder of 100mg then, ultrasonic 10min, magnetic agitation 10 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion that displaces three times.Add 30mL water, add 5g vulcanized sodium then, after ultrasonic 30 minutes, magnetic agitation 24h.Deposition staticly settles outwells clear liquid last time, repeats to wash three times, and evaporate to dryness under 100 ℃ of air atmospheres can obtain product.Its pattern and structure, and performance is shown in Fig. 1-6 and table 1.
Can find out that by Fig. 1 zinc powder is the bead of diameter less than 10 μ m, rough surface (Fig. 1 a, b).As the metal Cd that generates bar-shaped pattern with Cd solion displacement Zn; And the ZnO shell that can not be replaced is torn to shreds the surface that be distributed in metal Cd rod; This intermediateness is named as Cd-ZnO (shown in Fig. 1 c and d), and it not quite still is bar-shaped (shown in Fig. 1 e and f) that Cd-ZnO&CdS changes with respect to the macro morphology of the Cd-ZnO of vulcanizing treatment not.
Can be found out that by Fig. 2 the forming process of Cd-ZnO&CdS at first forms the Cd-ZnO intermediate with Cd ion exchange Zn, sulfuration forms the shell of CdS then, promptly is prepared into Cd-ZnO&CdS.
Can be found out that by Fig. 3 the macro morphology of Cd-ZnO&CdS is mainly bar-shaped, it is inner to be Cd nuclear, the surperficial shell of inlaying the ZnO particle for CdS.In the present embodiment, the thickness of CdS shell is 20nm, and the ZnO granular size is 10nm.
Can be found out that by Fig. 4 its visible absorption of Zn-ZnO and Cd-ZnO powder is not very strong, behind sulfuration generation CdS, the visible absorption of Cd-ZnO&CdS strengthens gradually.
Can find out that by Fig. 5 the existence of CdS is arranged among the Cd-ZnO&CdS of sulfuration back.
Can find out by Fig. 6, the analysis result of the EDX of Cd-ZnO&CdS behind the load co-catalyst Pt, 1,2 and No. 3 all go up on the edge of the position, can find that tangible Zn is arranged, the existence of O, Cd, S and Pt element.
Table 1. different time Na
2The photocatalysis hydrogen-producing speed of the Cd-ZnO&CdS of S aqueous solution sulfuration preparation.
Can find out by table 1,, finally tend towards stability along with the increase hydrogen-producing speed of cure time increases gradually.
At first, the 1g caddy is dissolved in the 50mL water, adds the zinc powder of 200mg then, ultrasonic 30 minutes, magnetic agitation 20 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion that displaces three times.Add 50mL water, add 10g vulcanized sodium then, after ultrasonic 30 minutes, magnetic agitation 1h.Deposition staticly settles outwells clear liquid last time, repeats to wash three times, and evaporate to dryness under 60 ℃ of air atmospheres can obtain product.
At first, the 2g cadmium nitrate is dissolved in the 100mL water, adds the zinc powder of 500mg then, ultrasonic 10 minutes, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion that displaces three times.Add 200mL water, add 30g vulcanized sodium then, after ultrasonic 30 minutes, magnetic agitation 10h.Deposition staticly settles outwells clear liquid last time, repeats to wash three times, and evaporate to dryness under 80 ℃ of air atmospheres can obtain product.
Embodiment 4
At first, the 1g cadmium acetate is dissolved in the 40mL water, adds the zinc powder of 100mg then, ultrasonic 20 minutes, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion that displaces three times.Add 50mL water, add 5g vulcanized sodium then, after ultrasonic 10 minutes, magnetic agitation 4h.Deposition staticly settles outwells clear liquid last time, repeats to wash three times, and evaporate to dryness under 100 ℃ of air atmospheres can obtain product.
Embodiment 5
At first, the 1g cadmium acetate is dissolved in the 40mL water, adds the zinc powder of 100mg then, ultrasonic 20 minutes, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion that displaces three times.Change porcelain boat over to after 60 ℃ of air atmosphere oven dry, put into tube furnace, logical hydrogen sulfide 25mLmin
-1, 25 ℃ of curing temperatures, cure time are 2h.Stop to feed hydrogen sulfide then, logical argon gas is got rid of remaining hydrogen sulfide gas, promptly obtains product.
Embodiment 6
At first, the 1g caddy is dissolved in the 50mL water, adds the zinc powder of 200mg then, ultrasonic 10min, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion that displaces three times.Change porcelain boat over to after 60 ℃ of air atmosphere oven dry, put into tube furnace, logical hydrogen sulfide 50mL min
-1, 25 ℃ of curing temperatures, cure time are 2h.Stop to feed hydrogen sulfide then, logical argon gas is got rid of remaining hydrogen sulfide gas, promptly obtains product.
Embodiment 7
At first, the 1g caddy is dissolved in the 50mL water, adds the zinc powder of 200mg then, ultrasonic 10min, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion that displaces three times.Change porcelain boat over to after 60 ℃ of air atmosphere oven dry, put into tube furnace, earlier temperature is raised to 100 ℃, logical again hydrogen sulfide 25mL min
-1, cure time is 1h.Stop to feed hydrogen sulfide then, logical argon gas is got rid of remaining hydrogen sulfide gas, promptly obtains product.
Embodiment 8
At first, the 0.5g caddy is dissolved in the 50mL water, adds the zinc powder of 100mg then, ultrasonic 30min, magnetic agitation 20 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion that displaces three times.Add 50mL water, add the 5g potassium sulfide then, after ultrasonic 30 minutes, magnetic agitation 2h.Deposition staticly settles outwells clear liquid last time, repeats to wash three times, and evaporate to dryness under 60 ℃ of air atmospheres can obtain product.
Embodiment result shows that metal core catalyst of the present invention has very high photocatalytic hydrogen production by water decomposition ability, and hydrogen-producing speed can reach 23mol h
-1g
-1, be expected to be applied at the decomposing water with solar energy hydrogen preparation field.
Claims (10)
1. one kind is the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure; It is characterized in that: cadmium metal is nuclear; Semiconductor heterostructure zinc oxide and cadmium sulfide are shell; The shared molar ratio of cadmium metal is 50%～90%, and the shared molar ratio of zinc oxide is 5%, and the shared molar ratio of cadmium sulfide is 5%～45%.
2. described according to claim 1 is the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure; It is characterized in that: semiconductor heterostructure zinc oxide and cadmium sulfide are shell; Be meant the surperficial shell of inlaying Zinc oxide particles for cadmium sulfide; The thickness of cadmium sulfide shell is 5-50nm, and the Zinc oxide particles size is 3-50nm.
3. described according to claim 1 is the preparation method of the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure; It is characterized in that: zinc powder is a presoma; Generate cadmium sulfide shell process through the sulfuration of cadmium ion displacement reaction; Obtaining with the cadmium metal is nuclear, and semiconductor heterostructure zinc oxide and cadmium sulfide are the photocatalytic hydrogen production by water decomposition catalyst of shell.
4. described according to claim 1 is the preparation method of the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure; It is characterized in that: at first will contain the cadmium ion presoma and be dissolved in the deionized water; Add then zinc powder ultrasonic with the magnetic agitation condition under, cadmium ion displacement metallic zinc; After the washing, add sulphurizing salt aqueous solution vulcanizing treatment, or oven dry back use hydrogen sulfide gas vulcanizing treatment, obtaining product for being nuclear with the cadmium metal, semiconductor heterostructure zinc oxide and cadmium sulfide are the composite photocatalyst of shell.
5. described according to claim 4 is the preparation method of the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure; It is characterized in that: contain the cadmium ion presoma and be a kind of of caddy, cadmium nitrate, cadmium acetate, the concentration range of its aqueous solution is 0.03～0.5mol L
-1
6. described according to claim 4 is the preparation method of the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure, and it is characterized in that: zinc particle is of a size of 5～200 μ m.
7. described according to claim 4 is the preparation method of the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure, it is characterized in that: the ultrasonic time of cadmium ion displacement metallic zinc is 10min～1h, and the magnetic agitation time is 10min～2h.
8. described according to claim 4 is the preparation method of the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure, and it is characterized in that: the sulphurizing salt that vulcanizing treatment adopts is a kind of of vulcanized sodium or potassium sulfide, and the concentration of its aqueous solution is 0.1～2mol L
-1, curing time is 0.5～48h, sulfuration after washing number of times 2～5 times, and the product bake out temperature is 50～120 ℃.
9. described according to claim 4 is the preparation method of the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure, and it is characterized in that: vulcanizing treatment adopts hydrogen sulfide, and the hydrogen sulfide gas flow is 5～100mL min
-1, curing temperature is 25～300 ℃.
10. described according to claim 4 is the preparation method of the composite photocatalyst of shell with the cadmium metal for the dyskaryosis structure; It is characterized in that: products therefrom is made up of cadmium metal nuclear, zinc oxide and cadmium sulfide shell, and its molar ratio is between 50: 5: 45 to 90: 5: 5; Particle is mainly bar-shaped, diameter 100nm～2 μ m, length 300nm～20 μ m.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103240103A (en) * | 2013-04-27 | 2013-08-14 | 辽宁石油化工大学 | Method for preparing cadmium sulfide sensitized zinc oxide heterojunction photocatalyst by combination of ionic liquid and ultrasonic treatment |
| CN103316693A (en) * | 2013-07-03 | 2013-09-25 | 西北师范大学 | Photocatalyst Cd/CdS containing catalyst promoter Cd as well as preparation method and application of photocatalyst Cd/CdS in photocatalysis hydrogen production reaction |
| CN105498802A (en) * | 2015-12-04 | 2016-04-20 | 福州大学 | ZnO-Au-CdS ternary composite photocatalyst |
| CN104549270B (en) * | 2013-10-15 | 2017-02-22 | 中国科学院金属研究所 | Heterogeneous p-n knot nano composite material and preparation method and application thereof |
| CN108786854A (en) * | 2017-05-06 | 2018-11-13 | 佛山市洁灏环保科技有限公司 | A kind of compound cadmium sulfide photochemical catalyst |
| CN115888759A (en) * | 2022-11-15 | 2023-04-04 | 南昌大学 | Synthesis method of alternately bridged cadmium sulfide-zinc oxide heterojunction periodic macroporous photocatalytic hydrogen evolution material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502793A (en) * | 2009-02-18 | 2009-08-12 | 吉林大学 | Method for preparing ZnO and CdO heterogeneous nanostructured oxide material |
| CN101590413A (en) * | 2009-06-26 | 2009-12-02 | 天津工业大学 | Has visible light-responded Zinc-cadmium sulfide photocatalyst and preparation method thereof |
-
2011
- 2011-02-16 CN CN201110039337.XA patent/CN102641741B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502793A (en) * | 2009-02-18 | 2009-08-12 | 吉林大学 | Method for preparing ZnO and CdO heterogeneous nanostructured oxide material |
| CN101590413A (en) * | 2009-06-26 | 2009-12-02 | 天津工业大学 | Has visible light-responded Zinc-cadmium sulfide photocatalyst and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 《international journal of hydrogen energy》 20100106 Xuewen Wang et al. Stable photocatalytic hydrogen evolution from water over ZnO-CdS core-shell nanorods 第8201页第2节 1-10 第35卷, * |
| FADI ALDEEK ET AL.: "Enhanced Optical Properties of Core/Shell/Shell CdTe/CdS/ZnO Quantum Dots Prepared in Aqueous Solution", 《J. PHYS. CHEM. C》 * |
| FADI ALDEEK ET AL.: "Enhanced Photostability from CdSe(S)/ZnO Core/Shell Quantum Dots and Their Use in Biolabeling", 《EUR. J. INORG. CHEM.》 * |
| XUEWEN WANG ET AL.: "Stable photocatalytic hydrogen evolution from water over ZnO–CdS core–shell nanorods", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
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| CN103316693A (en) * | 2013-07-03 | 2013-09-25 | 西北师范大学 | Photocatalyst Cd/CdS containing catalyst promoter Cd as well as preparation method and application of photocatalyst Cd/CdS in photocatalysis hydrogen production reaction |
| CN104549270B (en) * | 2013-10-15 | 2017-02-22 | 中国科学院金属研究所 | Heterogeneous p-n knot nano composite material and preparation method and application thereof |
| CN105498802A (en) * | 2015-12-04 | 2016-04-20 | 福州大学 | ZnO-Au-CdS ternary composite photocatalyst |
| CN105498802B (en) * | 2015-12-04 | 2017-12-08 | 福州大学 | A kind of zinc oxide gold cadmium sulfide ternary composite type photochemical catalyst |
| CN108786854A (en) * | 2017-05-06 | 2018-11-13 | 佛山市洁灏环保科技有限公司 | A kind of compound cadmium sulfide photochemical catalyst |
| CN115888759A (en) * | 2022-11-15 | 2023-04-04 | 南昌大学 | Synthesis method of alternately bridged cadmium sulfide-zinc oxide heterojunction periodic macroporous photocatalytic hydrogen evolution material |
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