CN105289656A - Solid solution catalyst for photocatalytic decomposition of water to produce hydrogen, and preparation method thereof - Google Patents
Solid solution catalyst for photocatalytic decomposition of water to produce hydrogen, and preparation method thereof Download PDFInfo
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- CN105289656A CN105289656A CN201510827154.2A CN201510827154A CN105289656A CN 105289656 A CN105289656 A CN 105289656A CN 201510827154 A CN201510827154 A CN 201510827154A CN 105289656 A CN105289656 A CN 105289656A
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- Prior art keywords
- zinc
- cadmium sulfide
- gram
- solid solution
- mol
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 44
- 239000006104 solid solution Substances 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- 238000005984 hydrogenation reaction Methods 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 97
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 74
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 29
- 239000010941 cobalt Substances 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 29
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000004246 zinc acetate Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000007146 photocatalysis Methods 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 45
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 28
- 238000006555 catalytic reaction Methods 0.000 description 16
- 238000001514 detection method Methods 0.000 description 16
- 239000003205 fragrance Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229910052724 xenon Inorganic materials 0.000 description 15
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 14
- 239000005083 Zinc sulfide Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 10
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical group [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
一种表面负载单质镍和钴的光催化分解水产氢固溶体催化剂及其制备方法，属于光催化剂技术领域。本发明所述高效光催化分解水产氢催化剂，是由乙酸铜和乙酸锌溶于去离子水中，然后加入硫化钠形成固溶体前躯体，再装进反应釜在一定温度下反应一定时间，最后将产物洗涤、干燥得产物硫化锌镉；接着再在硫化锌镉表面负载上金属镍和钴。本发明可以使光催化分解水产氢反应速率由纯硫化锌镉的78130μmol？h-1g-1提高到211417μmol？h-1g-1，性能提高超过了2倍多。因此本发明是一种具有解决能源危机的工业应用性，并且是一种生产环保新型能源的新技术手段。
The invention discloses a solid solution catalyst for photocatalytic decomposition of water to generate hydrogen with elemental nickel and cobalt loaded on the surface and a preparation method thereof, belonging to the technical field of photocatalysts. The high-efficiency photocatalytic decomposition of water hydrogen production catalyst described in the present invention is to dissolve copper acetate and zinc acetate in deionized water, then add sodium sulfide to form a solid solution precursor, then put it into a reactor and react at a certain temperature for a certain period of time, and finally the product Washing and drying to obtain the zinc cadmium sulfide product; and then loading metal nickel and cobalt on the surface of the zinc cadmium sulfide. The invention can make the reaction rate of photocatalytic decomposition of water to produce hydrogen from 78130 μmol of pure zinc cadmium sulfide? h -1 g -1 increased to 211417 μmol? h -1 g -1 , the performance improvement is more than 2 times. Therefore, the present invention has industrial applicability for solving the energy crisis, and is a new technical means for producing environmentally friendly new energy.
Description
Technical field
The invention belongs to photocatalyst technology field, be specifically related to photocatalysis Decomposition aquatic products hydrogen solid solution catalyst of a kind of novel zinc-cadmium sulfide solid solution area load elemental nickel and cobalt and preparation method thereof.
Background technology
Zinc sulphide and cadmium sulfide are all the semi-conducting materials with photocatalysis performance, abundance and relative low price on earth, but the efficiency of the two photocatalysis Decomposition aquatic products hydrogen own is all very low, this is not mainly because the light induced electron be excited in semiconductor when being subject to illumination is effectively separated with hole, the overwhelming majority is all again be compounded with, the proton that the light induced electron produced can not shift in feedwater produces hydrogen, and this just causes the waste of great light resources.
In order to improve the performance of the photocatalysis Decomposition aquatic products hydrogen of zinc sulphide and cadmium sulfide, zinc-cadmium sulfide solid solution has just been found out, make zinc sulphide and cadmium sulfide form a solid solution by new synthesizing mean exactly and form hetero-junctions therein, this will be conducive to the separative efficiency of the photogenerated charge being excited generation by illumination, thus improve the performance of its photochemical catalyzing, but by further research we but to find that although the Photocatalyzed Hydrogen Production performance of the relatively each simple phase of solid solution increases still efficient not, be difficult to meet industrial requirement, so also need to make improvements and design.
Summary of the invention
In order to the problem that the photochemical catalyzing hydrogen generation efficiency solving zinc-cadmium sulfide solid solution catalyst existence in prior art is lower, the mechanism of the present invention to zinc-cadmium sulfide solid solution photocatalysis Decomposition aquatic products hydrogen conducts in-depth research, after having paid a large amount of original works, and then complete the present invention.
High efficiency photocatalysis of the present invention decomposes aquatic products hydrogen catalyst, be dissolved in deionized water by cadmium acetate and zinc acetate different mol ratio example, then add vulcanized sodium and form solid solution precursor, refill and react certain hour at a certain temperature into reactor, finally product is washed, dry product zinc-cadmium sulfide hetero-junctions crystal; Then elemental nickel nano particle and simple substance cobalt nano particle on zinc-cadmium sulfide area load again.
The present invention can make photocatalysis Decomposition aquatic products hydroformylation reaction rate by pure zinc-cadmium sulfide 78130 micromoles/time/gram (μm olh
-1g
-1) bring up to 211417 micromoles/time/gram (μm olh
-1g
-1), performance raising has exceeded more than 2 times.Therefore the present invention be a kind of have solve energy crisis industrial applicability and be a kind of new technical means producing the environment-friendly novel energy.
A kind of high efficiency photocatalysis of the present invention decomposes the preparation method of aquatic products hydrogen catalyst, and its step is as follows:
(1) cadmium acetate of mol ratio 2 ~ 8:1 and zinc acetate solid particle is got in the reaction vessel filling 50 ~ 80 ml deionized water, the consumption of cadmium acetate is 0.05 ~ 0.4 gram, stirring after adding 0.7 ~ 1.5 gram of vulcanized sodium particle again makes it form even suspension for 1 ~ 6 hour, then transfer to and have in teflon-lined reactor, react 8 ~ 20 hours in the baking oven of 170 ~ 220 degrees Celsius again after reactor is sealed, take out reactor and make its at room temperature Temperature fall; (2) suspension obtained in step (1) reactor is spent deionized water centrifugal 3 ~ 5 times, again with centrifugal 1 ~ 3 time of ethanol washing, to abandon after supernatant under 80 ~ 100 degrees celsius dry 10 ~ 15 hours again, thus obtain zinc-cadmium sulfide solid solution;
(3) product getting step (2) gained disperses to form the zinc-cadmium sulfide suspension that concentration is 8 ~ 25 mg/litre in deionized water under any one gas shield that nitrogen, argon gas or nitrogen are argon-mixed, then successively add that volume is 1 ~ 10 milliliter, concentration is 0.0001 ~ 0.008 mol/L nickel nitrate solution and volume is 1 ~ 10 milliliter, concentration is 0.0001 ~ 0.008 mol/L cobalt nitrate solution, and stirs 1 ~ 6 hour wherein;
(4) in the product of step (3) gained, 0.1 ~ 0.9 gram of sodium borohydride granules is added, then stirring 1 ~ 6 hour is continued, then deionized water is spent centrifugal 3 ~ 5 times, again with centrifugal 1 ~ 2 time of ethanol washing, to abandon after supernatant under 80 ~ 100 degrees celsius dry 10 ~ 15 hours, obtain the zinc-cadmium sulfide solid solution of area load elemental nickel and simple substance cobalt, thus obtain photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention.
The test of luxuriant and rich with fragrance Lay light system for producing hydrogen and the detection of Japanese Shimadzu GC-81 type chromatograph is moored through Beijing, photochemical catalyst prepared by the present invention zinc-cadmium sulfide that catalysis photocatalytic water speed ratio is simple under vulcanized sodium, sodium sulfite and triethanolamine mixed liquor do the condition of sacrifice agent has had and has significantly improved, and the raising of performance has exceeded more than 2 times.
The present invention can make photochemical catalyzing efficiency greatly improve, and further meets industrial requirement.Composite catalyst system inhibits the compound in light induced electron and hole in zinc-cadmium sulfide under ultraviolet excitation greatly, improves the separative efficiency of photo-generated carrier, luminous energy is effectively utilized, and then improve the speed of its photochemical catalyzing.Therefore the present invention is very significant innovation and creation.
Accompanying drawing explanation
Fig. 1: (a) pure zinc-cadmium sulfide (zinc-cadmium sulfide (NiCo/ZnCdS (being called for short NC/ZCS) the hydrogen-producing speed phenogram of sample and the hydrogen-producing speed phenogram of (b) pure ZCS, ZnS, CdS sample and (c) sample Ni under different sacrifice agent condition of ZnCdS (being called for short ZCS) and load elemental nickel and simple substance cobalt
0.8co
0.2/ Zn
0.75cd
0.25the hydrogen-producing speed phenogram of S;
Clearly can find out that we are greatly improved than simple ZCS by modified sample hydrogen-producing speed from figure (a); Can also see that ZCS improves again a lot than simple ZnS, CdS H2-producing capacity from figure (b) simultaneously; Can find out that from figure (c) different sacrifice agents is very large to the performance impact of producing hydrogen, vulcanized sodium, sodium sulfite and triethanolamine are jointly optimum with the use of effect as sacrifice agent.
Fig. 2: Fig. 2 (a) and Fig. 2 (b) are sample Ni
0.8co
0.2/ Zn
0.75cd
0.25s transmission electron microscope picture; Fig. 2 (a) is the transmission electron microscope picture under low multiplication factor, and Fig. 2 (b) is the transmission electron microscope picture under high-resolution, can find out Ni from Fig. 2 (a)
0.8co
0.2/ Zn
0.75cd
0.25s is the monodispersed crystal of growth particle diameter, in Fig. 2 (b), and Zn
0.75cd
0.25s spacing of lattice (d), d=0.32nm correspond to Zn
0.75cd
0.25[111] crystal face of S, describes phase that ZnS and CdS is not individualism but defines a good solid solution.
Fig. 3: pure ZCS and NC/ZCS fluorescence spectrum phenogram; Photoluminescence spectrum intensity Ni
0.8co
0.2/ ZCS, Ni
0.5co
0.5/ ZCS, Co/ZCS and ZCS compare and greatly reduce, and the sample this demonstrating our compound inhibits the compound in light induced electron and hole greatly, thus improves the utilization ratio of luminous energy.
Fig. 4: sample N
0.8c
0.2element Surface scan (mapping) phenogram of/ZCS and tunnel scanning electron microscope diagram (SEM); Mapping figure is the pattern of corresponding SEM, directly shows all existence of Zn, Cd, S, Ni, Co element in composite sample and its distribution situation is also very clear, thus sample Ni, Co of having confirmed us have further loaded to ZnCdS surface uniformly.
Fig. 5: the phenogram of the X-ray diffractometer (XRD) of zinc sulphide (ZnS) and cadmium sulfide (CdS) and zinc-cadmium sulfide (ZnCdS); The characteristic peak as can be seen from the figure both in solid solution with zinc sulphide also has the characteristic peak of cadmium sulfide, and the characteristic peak of zinc sulphide is more obviously because zinc sulphide content is 3 times of cadmium sulfide in this solid solution, zinc sulphide and PDF card numbering corresponding to cadmium sulfide: 65-9585 and 41-1049.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Embodiment 1
(1) get 0.404 gram of zinc acetate (purity=99.5%) and 0.106 gram of cadmium acetate (purity=99.5%) to put into 250 ml beakers together and stir 10 minutes, then add the vulcanized sodium (purity=99.0%) of 0.829 gram under continuing stirring condition, continue stirring 4 hours; Then transfer to and have in teflon-lined reactor, the baking oven reaction of reactor being put into 180 degree was taken out reactor and is made its at room temperature Temperature fall after 12 hours;
(2) suspension obtained in step (1) reactor is spent deionized water centrifugal 4 times, then use ethanol (purity=99.9%) to wash centrifugal 2 times, to abandon after supernatant drier 12 hours at 80 degrees celsius; Namely the product obtained after drying is our zinc-cadmium sulfide solid solution Zn to be prepared
0.75cd
0.25s, is detected as the zinc-cadmium sulfide solid solution of pure phase through X-ray diffractometer (XRD);
(3) product in step (2) is mixed to form even suspension (pure phase Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution, 5 milliliters of mass fractions of the sodium sulfide solution of S0.05 gram, 45 milliliter 0.35 mol/L, 45 milliliter of 0.25 mol/L are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Zn prepared by the present invention
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 78130 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 8 phase specific hydrogen production rate.
Embodiment 2
Step (1) ~ (2) are with embodiment 1;
(3) product getting step (2) gained is dispersed in 20 ml deionized water under nitrogen protection, adopts ultrasonic machine within ultrasonic 30 minutes, then to stir the cobalt nitrate solution successively adding 5 milliliter of 0.0046 mol/L prepared for 30 minutes and continues stirring 2 hours;
(4) in step (3), add sodium borohydride (purity=99.5%) particle of 0.36 gram, then stirring 5 hours is continued, then deionized water is spent centrifugal 5 times, ethanol (purity=99.9%) is used to wash centrifugal 2 times again, the zinc-cadmium sulfide solid solution of area load simple substance cobalt within dry 12 hours, is obtained at 80 degrees celsius after abandoning supernatant, namely the quality of photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention and simple substance cobalt accounts for the mass fraction of zinc-cadmium sulfide solid solution is 1%, called after: 1%Co/Zn
0.75cd
0.25s.
(5) product in step (4) is mixed to form even suspension (pure phase 1%Co/Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution, 5 milliliters of mass fractions of the sodium sulfide solution of S0.05 gram, 45 milliliter 0.35 mol/L, 45 milliliter of 0.25 mol/L are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure 1%Co/Zn prepared by the present invention
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 94926 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 8 phase specific hydrogen production rate.
Embodiment 3
Step (1) ~ (2) are with embodiment 1;
(3) product getting step (2) gained is dispersed in 20 ml deionized water under nitrogen protection, adopts ultrasonic machine within ultrasonic 30 minutes, then to stir the nickel nitrate solution successively adding 5 milliliter of 0.0046 mol/L prepared for 30 minutes and continues stirring 2 hours;
(4) in step (3), add sodium borohydride (purity=99.5%) particle of 0.36 gram, then stirring 5 hours is continued, then deionized water is spent centrifugal 5 times, ethanol (purity=99.9%) is used to wash centrifugal 2 times again, the zinc-cadmium sulfide solid solution of area load elemental nickel within dry 12 hours, is obtained at 80 degrees celsius after abandoning supernatant, namely the quality of photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention and elemental nickel accounts for the mass fraction of zinc-cadmium sulfide solid solution is 1%, called after: 1%Ni/Zn
0.75cd
0.25s.
(5) product in step (4) is mixed to form even suspension (pure phase 1%Ni/Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution, 5 milliliters of mass fractions of the sodium sulfide solution of S0.05 gram, 45 milliliter 0.35 mol/L, 0.25 mol/L of 45 milliliters are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure 1%Ni/Zn prepared by the present invention
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 143147 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 8 phase specific hydrogen production rate.
Embodiment 4
Step (1) ~ (2) are with embodiment 1;
(3) product getting step (2) gained is dispersed in 20 ml deionized water under nitrogen protection, and the cobalt nitrate solution adopting ultrasonic machine then to stir nickel nitrate solution and 4 milliliter of 0.0046 mol/L successively adding 1 milliliter of 0.0046 mol/L prepared for 30 minutes for ultrasonic 30 minutes continues stirring 2 hours;
(4) in step (3), add sodium borohydride (purity=99.5%) particle of 0.36 gram, then stirring 5 hours is continued, then deionized water is spent centrifugal 5 times, ethanol (purity=99.9%) is used to wash centrifugal 2 times again, the zinc-cadmium sulfide solid solution of area load elemental nickel simple substance cobalt within dry 12 hours, is obtained at 80 degrees celsius after abandoning supernatant, namely the mass fraction accounting for zinc-cadmium sulfide solid solution of the quality sum of photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention and elemental nickel and simple substance cobalt is 1% wherein elemental nickel: the mol ratio=0.2:0.8 of simple substance cobalt, called after: Ni
0.2co
0.8/ Zn
0.75cd
0.25s.
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.2co
0.8/ Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution and 5 milliliters of mass fractions of 0.25 mol/L of the sodium sulfide solution of S0.05 gram, 45 milliliter 0.35 mol/L and 45 milliliters are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Ni prepared by the present invention
0.2co
0.8/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 157280 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 8 phase specific hydrogen production rate.
Embodiment 5
Step (1) ~ (2) are with embodiment 1;
(3) product getting step (2) gained is dispersed in 20 ml deionized water under nitrogen protection, and the cobalt nitrate solution adopting ultrasonic machine then to stir nickel nitrate solution and 3 milliliter of 0.0046 mol/L successively adding 2 milliliter of 0.0046 mol/L prepared for 30 minutes for ultrasonic 30 minutes continues stirring 2 hours;
(4) in step (3), add sodium borohydride (purity=99.5%) particle of 0.36 gram, then stirring 5 hours is continued, then deionized water is spent centrifugal 5 times, ethanol (purity=99.9%) is used to wash centrifugal 2 times again, the zinc-cadmium sulfide solid solution of area load elemental nickel and simple substance cobalt within dry 12 hours, is obtained at 80 degrees celsius after abandoning supernatant, namely the mass fraction accounting for zinc-cadmium sulfide solid solution of the quality sum of photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention and elemental nickel and simple substance cobalt is 1% wherein elemental nickel: the mol ratio=0.4:0.6 of simple substance cobalt, called after: Ni
0.4co
0.6/ Zn
0.75cd
0.25s.
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.4co
0.6/ Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution, 5 milliliters of mass fractions of the sodium sulfide solution of S0.05 gram, 45 milliliter 0.35 mol/L, 0.25 mol/L of 45 milliliters are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Ni prepared by the present invention
0.4co
0.6/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 173707 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 8 phase specific hydrogen production rate.
Embodiment 6
Step (1) ~ (2) are with embodiment 1;
(3) product getting step (2) gained is dispersed in 20 ml deionized water under nitrogen protection, and the cobalt nitrate solution adopting ultrasonic machine then to stir nickel nitrate solution and 2.5 milliliter of 0.0046 mol/L successively adding 2.5 milliliter of 0.0046 mol/L prepared for 30 minutes for ultrasonic 30 minutes continues stirring 2 hours;
(4) in step (3), add sodium borohydride (purity=99.5%) particle of 0.36 gram, then stirring 5 hours is continued, then deionized water is spent centrifugal 5 times, ethanol (purity=99.9%) is used to wash centrifugal 2 times again, the zinc-cadmium sulfide solid solution of area load elemental nickel and simple substance cobalt within dry 12 hours, is obtained at 80 degrees celsius after abandoning supernatant, namely the mass fraction accounting for zinc-cadmium sulfide solid solution of the quality sum of photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention and elemental nickel and simple substance cobalt is 1% wherein elemental nickel: the mol ratio=0.5:0.5 of simple substance cobalt, called after: Ni
0.5co
0.5/ Zn
0.75cd
0.25s.
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.5co
0.5/ Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution, 5 milliliters of mass fractions of the sodium sulfide solution of S0.05 gram, 45 milliliter 0.35 mol/L, 0.25 mol/L of 45 milliliters are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Ni prepared by the present invention
0.5co
0.5/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 188999 micromoles/time/gram (μm olh
-1g
-1); Slightly low with embodiment 8 phase specific hydrogen production rate.
Embodiment 7
Step (1) ~ (2) are with embodiment 1;
(3) product getting step (2) gained is dispersed in 20 ml deionized water under nitrogen protection, and the cobalt nitrate solution adopting ultrasonic machine then to stir nickel nitrate solution and 2 milliliter of 0.0046 mol/L successively adding 3 milliliter of 0.0046 mol/L prepared for 30 minutes for ultrasonic 30 minutes continues stirring 2 hours;
(4) in step (3), add sodium borohydride (purity=99.5%) particle of 0.36 gram, then stirring 5 hours is continued, then deionized water is spent centrifugal 5 times, ethanol (purity=99.9%) is used to wash centrifugal 2 times again, the zinc-cadmium sulfide solid solution of area load elemental nickel and simple substance cobalt within dry 12 hours, is obtained at 80 degrees celsius after abandoning supernatant, namely the mass fraction accounting for zinc-cadmium sulfide solid solution of the quality sum of photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention and elemental nickel and simple substance cobalt is 1% wherein elemental nickel: the mol ratio=0.6:0.4 of simple substance cobalt, called after: Ni
0.6co
0.4/ Zn
0.75cd
0.25s.
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.6co
0.4/ Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution, 5 milliliters of mass fractions of the sodium sulfide solution of S0.05 gram, 45 milliliter 0.35 mol/L, 0.25 mol/L of 45 milliliters are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Ni prepared by the present invention
0.6co
0.4/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 191399 micromoles/time/gram (μm olh
-1g
-1); Slightly low with embodiment 8 phase specific hydrogen production rate.
Embodiment 8
Step (1) ~ (2) are with embodiment 1;
(3) product getting step (2) gained is dispersed in 20 ml deionized water under nitrogen protection, and the cobalt nitrate solution adopting ultrasonic machine then to stir nickel nitrate solution and 1 milliliter of 0.0046 mol/L successively adding 4 milliliter of 0.0046 mol/L prepared for 30 minutes for ultrasonic 30 minutes continues stirring 2 hours;
(4) in step (3), add sodium borohydride (purity=99.5%) particle of 0.36 gram, then stirring 5 hours is continued, then deionized water is spent centrifugal 5 times, ethanol (purity=99.9%) is used to wash centrifugal 2 times again, the zinc-cadmium sulfide solid solution of area load elemental nickel and simple substance cobalt within dry 12 hours, is obtained at 80 degrees celsius after abandoning supernatant, namely the mass fraction accounting for zinc-cadmium sulfide solid solution of the quality sum of photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention and elemental nickel and simple substance cobalt is 1% wherein elemental nickel: the mol ratio=0.8:0.2 of simple substance cobalt, called after: Ni
0.8co
0.2/ Zn
0.75cd
0.25s.
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.8co
0.2/ Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution, 5 milliliters of mass fractions of the sodium sulfide solution of S0.05 gram, 45 milliliter 0.35 mol/L, 0.25 mol/L of 45 milliliters are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Ni prepared by the present invention
0.8co
0.2/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 211417 micromoles/time/gram (μm olh
-1g
-1).
Embodiment 9
Step (1) ~ (2) are with embodiment 1;
(3) product getting step (2) gained is dispersed in 20 ml deionized water under nitrogen protection, adopts ultrasonic 30 minutes of ultrasonic machine then to stir within 30 minutes, successively to add 5 milliliter of 0.0046 mol/L chloroplatinic acid (purity=99.5%) solution prepared to continue stirring 2 hours;
(4) in step (3), add sodium borohydride (purity=99.5%) particle of 0.36 gram, then stirring 5 hours is continued, then deionized water is spent centrifugal 5 times, ethanol (purity=99.9%) is used to wash centrifugal 2 times again, the zinc-cadmium sulfide solid solution of area load platinum within dry 12 hours, is obtained at 80 degrees celsius after abandoning supernatant, namely the quality of photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention and simple substance platinum accounts for the mass fraction of solid solution zinc-cadmium sulfide is 1%, called after: 1%Pt/Zn
0.75cd
0.25s.
(5) product in step (4) is mixed to form even suspension (pure phase 1%Pt/Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution, 5 milliliters of mass fractions of the sodium sulfide solution of S0.05 gram, 45 milliliter 0.35 mol/L, 0.25 mol/L of 45 milliliters are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure 1%Pt/Zn prepared by the present invention
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 136439 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 8 phase specific hydrogen production rate.
Embodiment 10
Step (1) ~ (4) are with embodiment 8;
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.8co
0.2/ Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution, 5 milliliters of mass fractions of the sodium sulfide solution of S0.025 gram, 45 milliliter 0.35 mol/L, 0.25 mol/L of 45 milliliters are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Ni prepared by the present invention
0.8co
0.2/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 364959 micromoles/time/gram (μm olh
-1g
-1).
Embodiment 11
Step (1) ~ (4) are with embodiment 8;
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.8co
0.2/ Zn
0.75cd
0.25sodium sulfite (purity=99.5%) aqueous solution of the sodium sulfide solution of S0.025 gram, 45 milliliter 0.35 mol/L, 0.25 mol/L of 45 milliliters), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Ni prepared by the present invention
0.8co
0.2/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 243124 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 10 phase specific hydrogen production rate.
Embodiment 12
Step (1) ~ (4) are with embodiment 8;
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.8co
0.2/ Zn
0.75cd
0.25the sodium sulfide solution of S0.025 gram, 45 milliliter 0.35 mol/L, 1 gram of disodium ethylene diamine tetraacetate (purity=99.5%) (being called for short " EDTA "), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Ni prepared by the present invention
0.8co
0.2/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 216123 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 10 phase specific hydrogen production rate.
Embodiment 13
Step (1) ~ (4) are with embodiment 8;
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.8co
0.2/ Zn
0.75cd
0.25s0.025 gram, 90 ml deionized water, 5 milliliters of mass fractions are the triethanolamine of 99.5%), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen through Beijing and irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph, pure Ni prepared by the present invention
0.8co
0.2/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 34698 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 10 phase specific hydrogen production rate.
Embodiment 14
Step (1) ~ (4) are with embodiment 8;
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.8co
0.2/ Zn
0.75cd
0.25s0.025 gram, 90 ml deionized water, 1 gram of disodium ethylene diamine tetraacetate (purity=99.5%) (being called for short " EDTA "), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen to irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing, pure Ni prepared by the present invention
0.8co
0.2/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 12935 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 10 phase specific hydrogen production rate.
Embodiment 15
Step (1) ~ (4) are with embodiment 8;
(5) product in step (4) is mixed to form even suspension (pure phase Ni
0.8co
0.2/ Zn
0.75cd
0.25s0.025 gram, 90 ml deionized water), moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen through Beijing and irradiate under the xenon lamp of 300 watts and the detection of Japanese Shimadzu GC-81 type chromatograph, pure Ni prepared by the present invention
0.8co
0.2/ Zn
0.75cd
0.25s catalysis photocatalytic water hydrogen-producing speed be 1785 micromoles/time/gram (μm olh
-1g
-1); Lower with embodiment 10 phase specific hydrogen production rate.
To sum up prepare example, we draw following conclusion further:
(1) mol ratio of elemental nickel and simple substance cobalt load has individual scope, i.e. the mole of elemental nickel: mole (Ni:Co)=0.2:0.8 ~ 0.8:0.2 of simple substance cobalt, and optimal value is: Ni:Co=0.8:0.2;
(2) the embodiment of the present invention 8 photocatalytic water H2-producing capacity of the photochemical catalyst of nickel-loaded cobalt prepared will far above Supported Pt Nanoparticles, and therefore the present invention can reduce light-catalysed cost greatly;
(3) adding of sacrifice agent triethanolamine, vulcanized sodium and sodium sulfite good synergy is played to photochemical catalyzing performance.
Claims (4)
1. high efficiency photocatalysis decomposes a preparation method for aquatic products hydrogen catalyst, and its step is as follows:
(1) cadmium acetate of mol ratio 2 ~ 8:1 and zinc acetate solid particle is got in the reaction vessel filling 50 ~ 80 ml deionized water, the consumption of cadmium acetate is 0.05 ~ 0.4 gram, stirring after adding 0.7 ~ 1.5 gram of vulcanized sodium particle again makes it form even suspension for 1 ~ 6 hour, then transfer to and have in teflon-lined reactor, react 8 ~ 20 hours in the baking oven of 170 ~ 220 degrees Celsius again after reactor is sealed, take out reactor and make its at room temperature Temperature fall;
(2) suspension obtained in step (1) reactor is spent deionized water centrifugal 3 ~ 5 times, again with centrifugal 1 ~ 3 time of ethanol washing, to abandon after supernatant under 80 ~ 100 degrees celsius dry 10 ~ 15 hours again, thus obtain zinc-cadmium sulfide solid solution;
(3) product getting step (2) gained disperses to form the zinc-cadmium sulfide suspension that concentration is 8 ~ 25 mg/litre in deionized water under any one gas shield that nitrogen, argon gas or nitrogen are argon-mixed, then successively add volume wherein and be 1 ~ 10 milliliter and concentration is that 0.0001 ~ 0.008 mol/L nickel nitrate solution and volume are 1 ~ 10 milliliter and concentration is 0.0001 ~ 0.008 mol/L cobalt nitrate solution, and stir 1 ~ 6 hour;
(4) in the product of step (3) gained, 0.1 ~ 0.9 gram of sodium borohydride granules is added, then stirring 1 ~ 6 hour is continued, then deionized water is spent centrifugal 3 ~ 5 times, again with centrifugal 1 ~ 2 time of ethanol washing, to abandon after supernatant under 80 ~ 100 degrees celsius dry 10 ~ 15 hours, obtain the zinc-cadmium sulfide solid solution of area load elemental nickel and simple substance cobalt, thus obtain photocatalysis Decomposition aquatic products hydrogen catalyst.
2. a kind of high efficiency photocatalysis as claimed in claim 1 decomposes the preparation method of aquatic products hydrogen catalyst, it is characterized in that: the mole of elemental nickel: the mole=0.2:0.8 ~ 0.8:0.2 of simple substance cobalt.
3. a kind of high efficiency photocatalysis as claimed in claim 1 decomposes the preparation method of aquatic products hydrogen catalyst, it is characterized in that: the mole of elemental nickel: the mole=0.8:0.2 of simple substance cobalt.
4. a photocatalysis Decomposition aquatic products hydrogen catalyst, is characterized in that: be prepared by the method for claims 1 to 3 described in any one.
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