CN102641741B - 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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- CN102641741B CN102641741B CN201110039337.XA CN201110039337A CN102641741B CN 102641741 B CN102641741 B CN 102641741B CN 201110039337 A CN201110039337 A CN 201110039337A CN 102641741 B CN102641741 B CN 102641741B
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- 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 6
- 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 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 15
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 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
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 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
- 238000006073 displacement reaction Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 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 8
- 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
- 239000007788 liquid Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000001556 precipitation Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 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
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 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
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 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
- 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
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 photochemical catalyst field, be specially and a kind ofly take cadmium metal as core, composite efficient photocatalytic hydrogen production by water decomposition catalyst and preparation method that zinc oxide and cadmium sulfide heterojunction structure are shell.
Background technology
A large amount of uses of fossil energy, bring serious environmental pollution on the one hand, and the carbon dioxide particularly producing after the burning of the carbon containing energy raises Global Temperature, 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 find a kind of clean energy capable of circulation, 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 clean hydrogen, just can not obtain by using fossil to transform.Utilize photocatalysis method by solar energy under the effect of photochemical catalyst, it is that a kind of ideal is effectively prepared hydrogen approach that water decomposition is produced to hydrogen.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.Conventionally in order to improve hydrogen-producing speed and to make end product only have hydrogen, can add the ion of catching oxygen as sacrifice agent.
In photocatalysis hydrogen production process research process, crucial problem is exactly the photochemical catalyst how designing with synthesizing efficient.At present, a large amount of existing photochemical catalysts mostly are single-phase photochemical catalyst, and efficiency is lower, and polynary plyability catalyst is not only conducive to the light abstraction width of extension system, more importantly can improve electronics after photocatalysis excites and the transfer in hole, thereby make catalysis system there is 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 composite catalyst.Zinc oxide and cadmium sulfide are a kind of catalyst of the compound photocatalytic hydrogen production by water decomposition shifting based on direct Z mechanism electronics, and not efficient as the transfer that affect photoexcitation carrier between the zinc oxide of hydrogen production efficiency performance-critical and cadmium sulfide, therefore need to design a kind of and cadmium metal is that core is with the polynary composite photo-catalyst of the new type structure of hud of carrier fast transfer between enhancing.
Summary of the invention
The object of the invention has been to provide a kind of catalyst and the preparation method of cadmium metal as core zinc oxide and the cadmium sulfide heterojunction structure composite efficient photocatalytic hydrogen production by water decomposition that is shell of take, solved the effectively problem of fast transfer of common composite catalyst zinc oxide and cadmium sulfide carrier, catalytic efficiency is significantly improved.
Technical scheme of the present invention is:
A kind ofly take the composite photocatalyst that cadmium metal is shell as dyskaryosis structure, cadmium metal is core, semiconductor heterostructure zinc oxide and cadmium sulfide are shell, the shared molar ratio of cadmium metal is 50%～90% (being preferably 60%～85%), the shared molar ratio of zinc oxide is 5%, and the shared molar ratio of cadmium sulfide is 5%～45% (being preferably 10%～35%).
In the present invention, semiconductor heterostructure zinc oxide and cadmium sulfide are shell, refer to that surface inlaying the shell of Zinc oxide particles for cadmium sulfide, and the thickness of cadmium sulfide shell is 5-50nm, and Zinc oxide particles size is 3-50nm.
The invention provides a kind of preparation method of cadmium metal as core zinc oxide and the cadmium sulfide heterojunction structure composite efficient photocatalytic hydrogen production by water decomposition catalyst that is shell of take.First will be dissolved in deionized water containing cadmium ion presoma, then add under the ultrasonic and magnetic agitation condition of zinc powder, cadmium ion displacement metallic zinc.Add sulphurizing salt aqueous solution vulcanizing treatment, or use hydrogen sulfide gas vulcanizing treatment after drying, obtain product for take the composite photocatalyst that cadmium metal is shell as core, zinc oxide and cadmium sulfide.Concrete being characterised in that wherein:
1, can be for caddy, cadmium nitrate, cadmium acetate containing cadmium ion presoma a kind of, the concentration range of its aqueous solution is 0.03～0.5mol L
-1.
2, the zinc particle adopting 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 adopting 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 product bake out temperature is 50～120 ℃.
5, adopt hydrogen sulfide: hydrogen sulfide gas flow is 5～100mL min
-1; Curing temperature is 25～300 ℃.
6, products therefrom is comprised of cadmium metal core 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 by cadmium ion and first forms cadmium-zinc oxide, and at cadmium metal superficial growth cadmium sulfide shell, has obtained cadmium metal core zinc oxide cadmium sulfide shell composite catalyst by sulfuration.This catalyst, in simulated solar photocatalysis Decomposition water hydrogen manufacturing test, has shown very high hydrogen-producing speed, shows equally very high yield hydrogen performance under the irradiation of natural daylight.Catalyst cadmium-Xin & Cadmium sulfide is introduced cadmium metal as the core of compound system by the method that ion replaces, the growth of original position cadmium sulfide is changed, and has solved the effectively problem of fast transfer of common composite catalyst zinc oxide and cadmium sulfide carrier, and catalytic efficiency is significantly improved.Thereby this composite photocatalyst is expected to be widely used in photocatalytic hydrogen production by water decomposition field.
Advantage of the present invention and beneficial effect are:
1, the present invention be take zinc powder as presoma, by cadmium ion, replace after zinc, sulfuration generates cadmium sulfide shell process, has obtained take cadmium metal as core, semiconductor heterostructure zinc oxide and cadmium sulfide are the high efficiency photocatalysis hydrogen production by water decomposition catalyst of shell, and maintenance has fine contact with original zinc oxide.
2, in the inventive method, cadmium sulfide is that surface in situ sulfuration at cadmium forms, so cadmium sulfide and cadmium core have fine adhesion.
3, the inventive method is introduced zinc oxide cadmium sulfide composite photocatalyst by cadmium metal core, and the carrier that excites that illumination generates can exchange fast by cadmium metal core, thereby strengthens the cooperative effect between composite catalyzing.
4, the thickness of the cadmium sulfide shell of the inventive method can be controlled by cure time, thereby arrives more excellent catalytic performance.
5, the inventive method is at room temperature synthesized this composite catalyst under condition, can save the energy.
Accompanying drawing explanation
Fig. 1. with the zinc powder (a) of zinc oxide shell and amplify the SEM photo of (b), cadmium-zinc oxide (c) after the growth of cadmium ion displacement zinc and amplify the SEM photo of (d) and with the cadmium-zinc oxide after sodium sulfide solution sulfuration and cadmium sulfide and amplify SEM photo; The insert pictures of c and e is its corresponding EDS collection of illustrative plates.
Fig. 2. the forming process schematic diagram 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 the cadmium-zinc oxide after vulcanizing treatment and cadmium sulfide (c).
Fig. 5. the XRD collection of illustrative plates of the cadmium-zinc oxide after sulfuration and cadmium sulfide.
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
Below in conjunction with embodiment, describe the present invention in detail.
Embodiment 1
First, 0.5g caddy is dissolved in 20mL water, then adds the zinc powder of 100mg, ultrasonic 10min, magnetic agitation 10 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion displacing three times.Add 30mL water, then add 5g vulcanized sodium, after ultrasonic 30 minutes, magnetic agitation 24h.Precipitation 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 as shown in Fig. 1-6 and table 1.
As seen from Figure 1, zinc powder is the bead that diameter is less than 10 μ m, rough surface (Fig. 1 a, b).When generate the metal Cd of Rod-like shape with Cd solion displacement Zn, and ZnO shell that can not be replaced is torn up the surface that be distributed in metal Cd rod, and this intermediateness is named as Cd-ZnO (as shown in Fig. 1 c and d), Cd-ZnO& It is not quite still bar-shaped (as shown in Fig. 1 e and f) that CdS changes with respect to the macro morphology of the Cd-ZnO of vulcanizing treatment not.
As seen from Figure 2, Cd-ZnO& The forming process of CdS, first forms Cd-ZnO intermediate with Cd ion exchange Zn, and then sulfuration forms the shell of CdS, is prepared into Cd-ZnO& CdS.
As seen from Figure 3, Cd-ZnO& The macro morphology of CdS is mainly bar-shaped, and its inside is Cd core, and the shell of ZnO particle is being inlayed for CdS in surface.In the present embodiment, the thickness of CdS shell is 20nm, and ZnO granular size is 10nm.
As seen from Figure 4, its visible absorption of Zn-ZnO and Cd-ZnO powder is not very strong, along with sulfuration generates after CdS, and Cd-ZnO& The visible absorption of CdS strengthens gradually.
As seen from Figure 5, Cd-ZnO& after sulfuration; In CdS, there is the existence of CdS.
As seen from Figure 6, Cd-ZnO& after load co-catalyst Pt; The analysis result of the EDX of CdS, on Jun edge, 1,2 and No. 3 position, can find that there is the existence of obvious Zn, O, Cd, S and Pt element.
Table 1. different time Na<sub TranNum="114">2</sub>the Cd-ZnO& of S aqueous solution sulfuration preparation; The Photocatalyzed Hydrogen Production speed of CdS.
As can be seen from Table 1, along with the increase hydrogen-producing speed of cure time increases gradually, finally tend towards stability.
First, 1g caddy is dissolved in 50mL water, then adds the zinc powder of 200mg, ultrasonic 30 minutes, magnetic agitation 20 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion displacing three times.Add 50mL water, then add 10g vulcanized sodium, after ultrasonic 30 minutes, magnetic agitation 1h.Precipitation 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 3
First, 2g cadmium nitrate is dissolved in 100mL water, then adds the zinc powder of 500mg, ultrasonic 10 minutes, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion displacing three times.Add 200mL water, then add 30g vulcanized sodium, after ultrasonic 30 minutes, magnetic agitation 10h.Precipitation 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
First, 1g cadmium acetate is dissolved in 40mL water, then adds the zinc powder of 100mg, ultrasonic 20 minutes, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion displacing three times.Add 50mL water, then add 5g vulcanized sodium, after ultrasonic 10 minutes, magnetic agitation 4h.Precipitation 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
First, 1g cadmium acetate is dissolved in 40mL water, then adds the zinc powder of 100mg, ultrasonic 20 minutes, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion displacing three times.60 ℃ of air atmospheres proceed to porcelain boat after drying, and put into tube furnace, logical hydrogen sulfide 25mLmin
-1, 25 ℃ of curing temperatures, cure time is 2h.Then stop passing into hydrogen sulfide, logical argon gas is got rid of remaining hydrogen sulfide gas, obtains product.
Embodiment 6
First, 1g caddy is dissolved in 50mL water, then adds the zinc powder of 200mg, ultrasonic 10min, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion displacing three times.60 ℃ of air atmospheres proceed to porcelain boat after drying, and put into tube furnace, logical hydrogen sulfide 50mL min
-1, 25 ℃ of curing temperatures, cure time is 2h.Then stop passing into hydrogen sulfide, logical argon gas is got rid of remaining hydrogen sulfide gas, obtains product.
Embodiment 7
First, 1g caddy is dissolved in 50mL water, then adds the zinc powder of 200mg, ultrasonic 10min, magnetic agitation 30 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion displacing three times.60 ℃ of air atmospheres proceed to porcelain boat after drying, and put into tube furnace, first temperature are raised to 100 ℃, more logical hydrogen sulfide 25mL min
-1, cure time is 1h.Then stop passing into hydrogen sulfide, logical argon gas is got rid of remaining hydrogen sulfide gas, obtains product.
Embodiment 8
First, 0.5g caddy is dissolved in 50mL water, then adds the zinc powder of 100mg, ultrasonic 30min, magnetic agitation 20 minutes, three times repeatedly.Staticly settle and outwell supernatant liquor, repeat to wash and remove the zinc ion displacing three times.Add 50mL water, then add 5g potassium sulfide, after ultrasonic 30 minutes, magnetic agitation 2h.Precipitation 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, 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 decomposing water with solar energy hydrogen preparation field.
Claims (7)
1. take the preparation method of cadmium metal as the dyskaryosis structure composite photocatalyst that is shell for one kind, it is characterized in that: in described composite photocatalyst, cadmium metal is core, semiconductor heterostructure zinc oxide and cadmium sulfide are shell, the shared molar ratio of cadmium metal is 50%～90%, the shared molar ratio of zinc oxide is 5%, and the shared molar ratio of cadmium sulfide is 5%～45%; Semiconductor heterostructure zinc oxide and cadmium sulfide are shell, refer to that surface inlaying the shell of Zinc oxide particles for cadmium sulfide, and the thickness of cadmium sulfide shell is 5-50nm, and Zinc oxide particles size is 3-50nm;
The preparation method of described composite photocatalyst be take zinc powder as presoma, by the sulfuration of cadmium ion displacement reaction, generates cadmium sulfide shell process, obtains take cadmium metal as core, the photocatalytic hydrogen production by water decomposition catalyst that semiconductor heterostructure zinc oxide and cadmium sulfide are shell; Be specially:
First will be dissolved in deionized water containing cadmium ion presoma, then add under the ultrasonic and magnetic agitation condition of zinc powder, cadmium ion displacement metallic zinc; After washing, add sulphurizing salt aqueous solution vulcanizing treatment, or use hydrogen sulfide gas vulcanizing treatment after drying, obtain product for take cadmium metal as core, the composite photocatalyst that semiconductor heterostructure zinc oxide and cadmium sulfide are shell.
2. according to claimed in claim 1, take the preparation method of cadmium metal as the dyskaryosis structure composite photocatalyst that is shell, it is characterized in that: containing cadmium ion presoma, be a kind of of caddy, cadmium nitrate, cadmium acetate, the concentration range of its aqueous solution is 0.03～0.5molL
-1.
3. according to claimed in claim 1, take the preparation method that cadmium metal is the dyskaryosis structure composite photocatalyst that is shell, it is characterized in that: zinc particle is of a size of 5～200 μ m.
4. according to claimed in claim 1, take the preparation method that cadmium metal is the dyskaryosis structure composite photocatalyst that is shell, 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.
5. according to claimed in claim 1, take the preparation method that cadmium metal is the dyskaryosis structure composite photocatalyst that is shell, 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 0.1～2molL
-1, curing time is 0.5～48h, sulfuration after washing number of times 2～5 times, and product bake out temperature is 50～120 ℃.
6. according to claimed in claim 1, take the preparation method that cadmium metal is the dyskaryosis structure composite photocatalyst that is shell, it is characterized in that: vulcanizing treatment adopts hydrogen sulfide, and hydrogen sulfide gas flow is 5～100mLmin
-1, curing temperature is 25～300 ℃.
7. according to claimed in claim 1, take the preparation method of cadmium metal as the dyskaryosis structure composite photocatalyst that is shell, it is characterized in that: products therefrom is comprised of cadmium metal core, zinc oxide and cadmium sulfide shell, its molar ratio at 50:5:45 between 90:5:5; Particle is mainly bar-shaped, diameter 100nm～2 μ m, length 300nm～20 μ m.
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| CN103316693B (en) * | 2013-07-03 | 2016-03-23 | 西北师范大学 | Containing the photochemical catalyst Cd/CdS of cocatalyst Cd and preparation thereof and the application in Photocatalyzed 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 |
| 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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