CN113209989A - Zinc cadmium sulfide nanorod and nickel nanorod heterojunction photocatalyst, preparation method thereof, hydrogen production system and hydrogen production method - Google Patents
Zinc cadmium sulfide nanorod and nickel nanorod heterojunction photocatalyst, preparation method thereof, hydrogen production system and hydrogen production method Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 90
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 90
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 69
- 239000002073 nanorod Substances 0.000 title claims abstract description 63
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 56
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000018417 cysteine Nutrition 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 150000001661 cadmium Chemical class 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 239000012265 solid product Substances 0.000 claims abstract description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 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
- 230000001678 irradiating effect Effects 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
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005286 illumination Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940065285 cadmium compound Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical group [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910021645 metal ion Chemical group 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of photocatalytic hydrogen production, and particularly relates to a zinc cadmium sulfide nanorod and nickel nanorod heterojunction hydrogen production photocatalyst, a preparation method thereof, a hydrogen production system and a hydrogen production method. The method comprises the following steps: 1) mixing zinc salt, cadmium salt, ethanolamine, cysteine and urea aqueous solution at room temperature, then carrying out hydrothermal reaction, and separating the obtained solid product to obtain a zinc cadmium sulfide nanorod; 2) dispersing the zinc cadmium sulfide nanorod obtained in the step 1) in an aqueous solution of polyethylene glycol and nickel sulfate, adding urea and hydrazine hydrate, and then carrying out hydrothermal reaction to obtain the heterojunction hydrogen photocatalyst of the zinc cadmium sulfide nanorod and the metal nickel nanorod. The proposal organically combines the semiconductor photocatalyst and the hydrogen production promoter into a heterojunction material to form the high-efficiency hydrogen production photocatalyst.
Description
Technical Field
The invention belongs to the technical field of photocatalytic hydrogen production, and particularly relates to a zinc cadmium sulfide nanorod and nickel nanorod heterojunction hydrogen production photocatalyst, a preparation method thereof, a hydrogen production system and a hydrogen production method.
Background
With the rapid development of socioeconomic, the existing fossil energy is far from meeting the increasing energy demand of human beings. The solar light is used for decomposing water to prepare hydrogen, which is an effective way for solving the problem. The renewable hydrogen energy has the excellent characteristics of no toxicity, zero emission after combustion, high specific energy value and the like, and is considered as the next generation of ideal alternative energy. The principle of hydrogen production by photolysis of water is that light irradiates on a semiconductor catalyst, when the light energy is larger than the forbidden bandwidth of the catalyst, electron and hole separation occurs, photo-generated electrons generated by the catalyst reduce water into hydrogen, and meanwhile, photo-generated holes are neutralized by a sacrificial reagent, so that the hydrogen is produced.
In the photocatalytic hydrogen production system widely researched at present, the photocatalytic efficiency of the semiconductor photocatalyst is generally low. Most of the platinum (Pt) with nanometer size is added as a cocatalyst to achieve higher photocatalytic efficiency, but the platinum (Pt) is expensive and is not suitable for large-scale industrial production. Therefore, the development of efficient and cheap composite photocatalysts without noble metal promoters is the main trend of the current research on the water photolysis catalysts. The development of efficient and stable photocatalysts is still the key to the practical application of hydrogen production by water decomposition. Of the numerous photocatalytic materials, cadmium zinc sulfide acts as a visible light responsive photocatalyst in comparison to other photocatalysts (e.g., TiO)2、g-C3N4Etc.) has good photocatalytic hydrogen production capacity, but the photo-generated electrons and holes are easy to be combined, and the photo-corrosion is easy to occur, the stability is poor, and in order to promote the rapid transfer of current carriers and prevent the photo-corrosion, the stability and the photocatalytic performance of the material can be improved by constructing a heterostructure.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a zinc cadmium sulfide nanorod and nickel nanorod heterojunction hydrogen production photocatalyst, a preparation method thereof, a hydrogen production system and a hydrogen production method. The zinc cadmium sulfide nanorod-metal nickel nano heterojunction prepared by the method has the advantages of large specific surface area, high stability and ultrahigh photocatalytic hydrogen production efficiency.
The technical scheme provided by the invention is as follows:
a preparation method of a zinc cadmium sulfide nanorod and metal nickel nanorod heterojunction hydrogen production photocatalyst comprises the following steps:
1) mixing zinc salt, cadmium salt, ethanolamine, cysteine and urea aqueous solution at room temperature, then carrying out hydrothermal reaction, and carrying out solid-liquid separation on the obtained product to obtain a solid product, namely the zinc-cadmium sulfide nanorod;
2) dispersing the zinc cadmium sulfide nanorods obtained in the step 1) in an aqueous solution of polyethylene glycol and nickel sulfate, adding urea and hydrazine hydrate, then carrying out hydrothermal reaction, and carrying out solid-liquid separation on the obtained product to obtain a solid product, namely the zinc cadmium sulfide nanorods and the metal nickel nanorods heterojunction hydrogen production photocatalyst.
In the above technical scheme:
in the step 1), cysteine and metal ions form cysteine-zinc and cysteine-cadmium compounds at room temperature, and can form soluble complex compounds in the presence of ethanolamine, during the hydrothermal reaction, the cysteine-zinc-cadmium compounds are simultaneously decomposed to form zinc-cadmium sulfide eutectic compounds, and zinc-cadmium sulfide nanocrystals directionally grow to form nanorod materials under the synergistic effect of ammonia water serving as a urea decomposition product and ethanolamine;
in the step 2), in the reaction, the urea is decomposed to generate ammonia water and nickel sulfate to form nickel hydroxide, nickel elementary substance atoms are formed under the reduction action of hydrazine hydrate, the nickel atoms are gathered on the surface of the zinc cadmium sulfide nanorod to form nickel nanoparticles, and the polyethylene glycol is used for inhibiting the independent formation of the nickel nanoparticles in the solution and ensuring the synthesis of the zinc cadmium sulfide nanorod-nickel nano heterojunction material.
Based on the scheme, the heterojunction of the zinc cadmium sulfide nanorod and the metal nickel nanorod can be obtained. Wherein, the nickel which is difficult to reduce is ensured to obtain the surrounding structure of the nano rod.
Specifically, in step 1):
the zinc salt is selected from any one or a mixture of zinc chloride, zinc acetate or zinc nitrate;
correspondingly, the cadmium salt is selected from any one or a mixture of cadmium chloride, cadmium acetate or cadmium nitrate;
the chemical composition of the obtained cadmium zinc sulfide nanorod is ZnxCd(1-x)S, wherein X is 0.4-0.6.
Specifically, in step 1):
the molar ratio of the zinc salt to the cadmium salt is 1 (0.67-1.5);
the ratio of the total molar weight of the zinc salt and the cadmium salt to the molar weight of the cysteine is 1 (2-4);
the volume ratio of the water to the ethanolamine is 1 (0.05-0.1);
in the obtained mixed solution, the content of urea is 0.1-1 wt%;
in the obtained mixed solution, the concentration of cysteine is 0.02-2.0 mol/L;
the temperature of the hydrothermal reaction is 160-180 ℃, and the time is 6-24 h.
Specifically, in the step 2):
zinc cadmium sulfide nanorod is ZnxCd(1-x)The molar ratio of S to nickel is 100 (1-8);
in the aqueous solution, the concentration of nickel sulfate is 0.002-0.2 wt%;
in the aqueous solution, the concentration of polyethylene glycol is 0.1-2 wt%;
the mass ratio of urea to nickel is (2-4) to 1;
the mass ratio of hydrazine hydrate to nickel is (2-4) to 1;
the temperature of the hydrothermal reaction is 85-100 ℃, and the time is 1-12 h.
The invention also provides a heterojunction hydrogen production photocatalyst of the zinc cadmium sulfide nanorod and the metal nickel nanorod prepared by the preparation method.
The invention also provides a hydrogen production system, which is a mixed liquid of the hydrogen production photocatalyst and a sacrificial agent, wherein the hydrogen production photocatalyst is selected from the zinc cadmium sulfide nanorod and the metal nickel nanorod heterojunction hydrogen production photocatalyst.
Specifically, the concentration of the zinc cadmium sulfide nanorod and the metal nickel nanorod heterojunction hydrogen production photocatalyst in the hydrogen production system is 0.05-1.0 g/L.
Specifically, the method comprises the following steps:
the concentration of the sacrificial agent is 0.2-2.0 mol/L;
the sacrificial agent is selected from Na2S and Na2SO3The complex aqueous solution of (1), an aqueous ascorbic acid solution, an aqueous glycolic acid solution or an aqueous triethanolamine solution.
The invention also provides a hydrogen production method, which comprises the following steps:
1) obtaining the hydrogen production system provided by the invention, and placing the hydrogen production system in a transparent sealing system under the protection of protective gas;
2) irradiating the sealed system obtained in the step 1) by using a light source to produce hydrogen.
Specifically, the light source is sunlight. The protective gas can be nitrogen, and is normal temperature and normal pressure.
The specific operation can be as follows:
1) weighing the prepared zinc cadmium sulfide nanorod-metallic nickel nano heterojunction photocatalyst, placing the zinc cadmium sulfide nanorod-metallic nickel nano heterojunction photocatalyst into a sealed transparent glass container with a stirrer, and adding an aqueous solution sacrificial agent (Na)2S-Na2SO3Mixing an aqueous solution, an aqueous solution of ascorbic acid, glycolic acid, triethanolamine, etc.), and stirring to uniformly disperse the catalyst in the mixed solution.
2) Introducing nitrogen to discharge residual gas in the container, irradiating the mixed solution containing the zinc cadmium sulfide nanorod-metal nickel nano heterojunction catalyst by light under the condition of uniform stirring, absorbing incident light energy by the zinc cadmium sulfide nanorod, generating photoproduction electron-hole separation, transferring electrons to the surface of the nano metal nickel, reducing hydrogen atoms by the action of the electrons and water, and separating out hydrogen, wherein the photoproduction hole is captured by a sacrificial agent. The generated hydrogen is collected by a pressure reduction system
The zinc cadmium sulfide nanorod and the metal nickel nano heterojunction material have high-efficiency water photolysis hydrogen production capacity, the hydrogen production amount reaches 100mmol/g/h under the irradiation of 1 standard sunlight, and the hydrogen production efficiency is 6-10 times higher than that of a conventional zinc cadmium sulfide material.
The invention has the beneficial effects that:
the photocatalyst is a zinc cadmium sulfide nanorod-metal nickel nano heterojunction composite material. The composite material organically combines the semiconductor photocatalyst and the hydrogen production promoter to form the high-efficiency hydrogen production photocatalyst, and the noble metal platinum and other promoters are not needed. The photocatalyst and the hydrogen production promoter nano metal nickel are combined together to form a heterojunction, so that the migration performance of photo-generated electrons can be effectively improved, and the recombination of the photo-generated electrons and holes is avoided. In addition, the nano metal nickel has very low hydrogen evolution potential, and is beneficial to improving the hydrogen production efficiency of the photocatalyst.
Drawings
FIG. 1 is a TEM image of hydrogen-producing photocatalyst provided by the present invention.
FIG. 2 is an XRD of the hydrogen-producing photocatalyst provided by the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
1) Dissolving 2mmol of cadmium chloride, 2mmol of zinc chloride, 0.4g of urea and 8mmol of cysteine in a mixed solution consisting of 70ml of water and 7ml of ethanolamine, uniformly stirring and mixing, placing the mixed solution in a hydrothermal reaction tank, reacting for 16h at 160 ℃ to obtain yellow precipitates, filtering, and washing with deionized water and ethanol for three times respectively to obtain Zn0.5Cd0.5And (3) an S nanorod photocatalyst.
2) 0.5g of Zn0.5Cd0.5The S nano-rod is dispersed in 100ml of distilled water by ultrasonic, and then 53mg of nickel sulfate, 100mg of polyethylene glycol (molecular weight 2000), 0.2g of urea and 1ml of hydrazine hydrate are added. After stirring and mixing evenly, the solution is transferred into a 200mL reaction kettle and reacted for 12h at the temperature of 95 ℃. Centrifugally separating the product, washing with deionized water and ethanol for 2 times respectively to obtain Zn0.5Cd0.5And (3) drying the S nanorod-metallic nickel nano heterojunction composite material in vacuum for later use.
3) 20mg of the above Zn was weighed0.5Cd0.5S nano rod-metallic nickel nano heterojunction photocatalyst is placed in a glass bottle with a magneton opening, and then 100mL of prepared 0.35M Na is added into the bottle2S-0.25M Na2S03The photocatalyst is dispersed by ultrasonic, then nitrogen is introduced for 5min, and finally the three-mouth glass bottle is sealed after being pumped. Placing the three-mouth glass bottle under a xenon lamp light source (simulating sunlight) for hydrogen production by illumination, and keeping electromagnetic stirring to disperse the photocatalyst in the hydrogen production process. The amount of hydrogen generated during the reaction was measured every 1 hour of light irradiation. The hydrogen yield was determined by gas chromatography. After 6 hours of visible light illumination, the hydrogen production of the system is stabilized at 1.8-2.2 mmol/h.
Example 2
1) Dissolving 12mmol of cadmium acetate, 8mmol of zinc acetate, 0.6g of urea and 50mmol of cysteine in a mixed solution consisting of 75ml of water and 4ml of ethanolamine, stirring and mixing uniformly, placing the mixed solution in a hydrothermal reaction tank, reacting for 6 hours at 180 ℃ to obtain yellow precipitates, filtering, washing with deionized water and ethanol for three times respectively to obtain Zn0.4Cd0.6And (3) an S nanorod photocatalyst.
2) 1.0g of Zn0.4Cd0.6The S nano-rod is dispersed in 100ml of distilled water by ultrasonic, and then 100mg of nickel sulfate, 200mg of polyethylene glycol (molecular weight 2000), 0.2g of urea and 1.5ml of hydrazine hydrate are added. After stirring and mixing evenly, the solution is transferred into a 200mL reaction kettle and reacted for 12h at 85 ℃. Centrifugally separating the product, washing with deionized water and ethanol for 2 times respectively to obtain Zn0.4Cd0.6And (3) drying the S nanorod-metallic nickel nano heterojunction composite material in vacuum for later use.
3) 20mg of the above Zn was weighed0.4Cd0.6The S nanorod-metallic nickel nano heterojunction photocatalyst is placed in a glass bottle with a magneton opening, 100mL of prepared 0.3M glycollic acid aqueous solution sacrificial agent is added into the bottle, the photocatalyst is dispersed by ultrasound, nitrogen is introduced for 5min, and finally the glass bottle with the opening is sealed after being pumped out. Placing the three-mouth glass bottle under a xenon lamp light source (simulating sunlight) for hydrogen production by illumination, and keeping electromagnetic stirring to disperse the photocatalyst in the hydrogen production process.The amount of hydrogen generated during the reaction was measured every 1 hour of light irradiation. The hydrogen yield was determined by gas chromatography. After 6 hours of visible light illumination, the hydrogen production of the system is stabilized at 1.6 mmol/h.
Example 3
1) Dissolving 8mmol of cadmium nitrate, 12mmol of zinc nitrate, 1.0g of urea and 40mmol of cysteine in a mixed solution consisting of 70ml of water and 7ml of ethanolamine, uniformly stirring and mixing, placing the mixed solution in a hydrothermal reaction tank, reacting for 8 hours at 170 ℃ to obtain yellow precipitates, filtering, and washing with deionized water and ethanol for three times respectively to obtain Zn0.6Cd0.4And (3) an S nanorod photocatalyst.
2) 1.0g of Zn0.6Cd0.4The S nano-rod is dispersed in 100ml of distilled water by ultrasonic, and then 300mg of nickel sulfate, 1.0g of polyethylene glycol (molecular weight 1000), 0.2g of urea and 10ml of hydrazine hydrate are added. After stirring and mixing evenly, the solution is transferred into a 200mL reaction kettle and reacts for 2h at the temperature of 100 ℃. Centrifugally separating the product, washing with deionized water and ethanol for 2 times respectively to obtain Zn0.6Cd0.4And (3) drying the S nanorod-metallic nickel nano heterojunction composite material in vacuum for later use.
3) 20mg of the above Zn was weighed0.6Cd0.4The S nanorod-metallic nickel nano heterojunction photocatalyst is placed in a glass bottle with a three-opening containing magnetons, 100mL of prepared 0.2M triethanolamine aqueous solution sacrificial agent is added into the bottle, the photocatalyst is dispersed ultrasonically, nitrogen is introduced for 5min, and finally the glass bottle with the three openings is sealed after being pumped out. Placing the three-mouth glass bottle under a xenon lamp light source (simulating sunlight) for hydrogen production by illumination, and keeping electromagnetic stirring to disperse the photocatalyst in the hydrogen production process. The amount of hydrogen generated during the reaction was measured every 1 hour of light irradiation. The hydrogen yield was determined by gas chromatography. After 6 hours of visible light illumination, the hydrogen production of the system is stabilized at 2.0 mmol/h.
Example 4
1) Dissolving 10mmol of cadmium acetate, 10mmol of zinc chloride, 0.7g of urea and 60mmol of cysteine in a mixed solution consisting of 73ml of water and 7ml of ethanolamine, stirring and mixing uniformly, placing the mixed solution in a hydrothermal reaction tank, reacting for 8 hours at 180 ℃,obtaining yellow precipitate, filtering, washing with deionized water and ethanol for three times respectively to obtain Zn0.5Cd0.5And (3) an S nanorod photocatalyst.
2) 1.0g of Zn0.5Cd0.5The S nano rod is dispersed in 100ml of distilled water by ultrasonic, and then 200mg of nickel sulfate, 2.0g of polyethylene glycol (molecular weight 1000), 0.2g of urea and 6ml of hydrazine hydrate are added. After stirring and mixing evenly, the solution is transferred into a 200mL reaction kettle. The reaction was carried out at 100 ℃ for 2 h. Centrifugally separating the product, washing with deionized water and ethanol for 2 times respectively to obtain Zn0.5Cd0.5And (3) drying the S nanorod-metallic nickel nano heterojunction composite material in vacuum for later use.
3) 20mg of the above Zn was weighed0.5Cd0.5S nano rod-metallic nickel nano heterojunction photocatalyst is placed in a glass bottle with a magneton opening, and then 100mL of prepared 0.35M Na is added into the bottle2S-0.25M Na2S03The photocatalyst is dispersed by ultrasonic, then nitrogen is introduced for 5min, and finally the three-mouth glass bottle is sealed after being pumped. Placing the three-mouth glass bottle under a xenon lamp light source (simulating sunlight) for hydrogen production by illumination, and keeping electromagnetic stirring to disperse the photocatalyst in the hydrogen production process. The amount of hydrogen generated during the reaction was measured every 1 hour of light irradiation. The hydrogen yield was determined by gas chromatography. After 6 hours of visible light illumination, the hydrogen production of the system is stabilized at 2.2 mmol/h.
As can be seen from FIG. 1, the hydrogen-producing photocatalyst obtained by the invention has a zinc-cadmium sulfide and nickel two-phase heterojunction structure. The cadmium zinc sulfide is of a nanorod structure, and the nickel is nanoparticles attached to the surface of the cadmium zinc sulfide nanorod.
The foregoing is merely a preferred embodiment of this invention and is not intended to limit the invention in any manner; those skilled in the art can readily practice the invention as shown and described in the drawings and detailed description herein; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention as defined by the appended claims; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a zinc cadmium sulfide nanorod and metal nickel nanorod heterojunction hydrogen production photocatalyst is characterized by comprising the following steps:
1) mixing zinc salt, cadmium salt, ethanolamine, cysteine and urea aqueous solution at room temperature, then carrying out hydrothermal reaction, and carrying out solid-liquid separation on the obtained product to obtain a solid product, namely the zinc-cadmium sulfide nanorod;
2) dispersing the zinc cadmium sulfide nanorods obtained in the step 1) in an aqueous solution of polyethylene glycol and nickel sulfate, adding urea and hydrazine hydrate, then carrying out hydrothermal reaction, and carrying out solid-liquid separation on the obtained product to obtain a solid product, namely the zinc cadmium sulfide nanorods and the metal nickel nanorods heterojunction hydrogen production photocatalyst.
2. The preparation method of the hydrogen production photocatalyst by the heterojunction of the cadmium zinc sulfide nanorod and the metal nickel nanorod according to claim 1, is characterized in that in the step 1):
the zinc salt is selected from any one or a mixture of zinc chloride, zinc acetate or zinc nitrate;
the cadmium salt is selected from any one or a mixture of cadmium chloride, cadmium acetate or cadmium nitrate;
the chemical composition of the obtained cadmium zinc sulfide nanorod is ZnxCd(1-x)S, wherein X is 0.4-0.6.
3. The preparation method of the hydrogen production photocatalyst by the heterojunction of the cadmium zinc sulfide nanorod and the metal nickel nanorod according to claim 1, is characterized in that in the step 1):
the molar ratio of the zinc salt to the cadmium salt is 1 (0.67-1.5);
the ratio of the total molar weight of the zinc salt and the cadmium salt to the molar weight of the cysteine is 1 (2-4);
the volume ratio of the water to the ethanolamine is 1 (0.05-0.1);
in the obtained mixed solution, the content of urea is 0.1-1 wt%;
in the obtained mixed solution, the concentration of cysteine is 0.02-2.0 mol/L;
the temperature of the hydrothermal reaction is 160-180 ℃, and the time is 6-24 h.
4. The preparation method of the hydrogen production photocatalyst by the heterojunction of the cadmium zinc sulfide nanorod and the metal nickel nanorod according to claim 1, wherein in the step 2):
zinc cadmium sulfide nanorod is ZnxCd(1-x)The molar ratio of S to nickel is 100 (1-8);
in the aqueous solution, the concentration of nickel sulfate is 0.002-0.2 wt%;
in the aqueous solution, the concentration of polyethylene glycol is 0.1-2 wt%;
the mass ratio of urea to nickel (2-4) is 1;
the mass ratio of hydrazine hydrate to nickel (2-4) is 1;
the temperature of the hydrothermal reaction is 85-100 ℃, and the time is 1-12 h.
5. The zinc cadmium sulfide nanorod and the metal nickel nanorod heterojunction hydrogen production photocatalyst prepared by the preparation method of any one of claims 1 to 4.
6. A hydrogen production system is a mixed aqueous solution of a hydrogen production photocatalyst and a sacrificial agent, and is characterized in that: the hydrogen production photocatalyst is selected from the zinc cadmium sulfide nanorod and metal nickel nanorod heterojunction hydrogen production photocatalyst in claim 5.
7. The hydrogen-generation system according to claim 6, characterized in that: the concentration of the zinc cadmium sulfide nanorod and the metal nickel nanorod heterojunction hydrogen production photocatalyst in the hydrogen production system is 0.05-1.0 g/L.
8. The hydrogen-generation system according to claim 6, characterized in that:
the sacrificial agent is selected from Na2S and Na2SO3The composite aqueous solution, the ascorbic acid aqueous solution, the glycolic acid aqueous solution or the triethanolamine aqueous solution of (1), wherein the concentration of the solute in the sacrificial agent is 0.2-2.0 mol/L.
9. A method for producing hydrogen, characterized by comprising the following steps:
1) obtaining the hydrogen production system of any one of claims 6 to 8 and placing the hydrogen production system in a transparent sealing system under the protection of protective gas;
2) irradiating the sealed system obtained in the step 1) by using a light source to produce hydrogen.
10. The hydrogen production method according to claim 9, characterized in that: the light source is sunlight.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113634267A (en) * | 2021-08-27 | 2021-11-12 | 西安交通大学 | CdS/ZnS-NiS nanocluster photocatalyst and preparation method and application thereof |
| CN113731424A (en) * | 2021-09-26 | 2021-12-03 | 青岛科技大学 | Zinc cadmium sulfur/nickel cobalt hydroxide composite visible light catalyst containing sulfur defects and application thereof |
| CN114618530A (en) * | 2022-02-16 | 2022-06-14 | 复旦大学 | NiS/Cd1-xZnxS goldenrain crystal nanorod composite photocatalyst and preparation method and application thereof |
| CN114713247A (en) * | 2022-03-31 | 2022-07-08 | 福州大学 | Nickel-coated sulfur-manganese-cadmium plasma photocatalyst rich in sulfur vacancy as well as preparation method and application thereof |
| CN114950486A (en) * | 2022-04-22 | 2022-08-30 | 北京科技大学 | Preparation method of bifunctional metal active site photocatalyst |
| CN115475645A (en) * | 2022-09-20 | 2022-12-16 | 厦门大学 | Oxidation catalyst and preparation method and application thereof |
| CN116273060A (en) * | 2023-03-01 | 2023-06-23 | 常州大学 | Preparation method and application of zinc cadmium sulfide and titanium carbide composite photocatalyst |
| WO2023246306A1 (en) * | 2023-02-15 | 2023-12-28 | 安徽科技学院 | Preparation method for cd0.5zn0.5s and experimental method for nitrogen fixation under photocatalysis thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289656A (en) * | 2015-11-25 | 2016-02-03 | 吉林大学 | Solid solution catalyst for photocatalytic decomposition of water to produce hydrogen, and preparation method thereof |
-
2021
- 2021-04-08 CN CN202110376070.7A patent/CN113209989A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289656A (en) * | 2015-11-25 | 2016-02-03 | 吉林大学 | Solid solution catalyst for photocatalytic decomposition of water to produce hydrogen, and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JINGANG SONG ET AL: "L-Cysteine assisted synthesis of Zn0.5Cd0.5S solid solution with different morphology, crystal structure and performance for H2 evolution", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| 廖铁星等, 广西师范大学出版社 * |
| 胡方能等: "多角金属纳米镍的化学液相制备、表征以及负载TiO2光催化研究", 《无机化学学报》 * |
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| CN113731424A (en) * | 2021-09-26 | 2021-12-03 | 青岛科技大学 | Zinc cadmium sulfur/nickel cobalt hydroxide composite visible light catalyst containing sulfur defects and application thereof |
| CN113731424B (en) * | 2021-09-26 | 2023-07-25 | 青岛科技大学 | Zinc-cadmium-sulfur/nickel-cobalt hydroxide composite visible light catalyst with sulfur-containing defect and application thereof |
| CN114618530A (en) * | 2022-02-16 | 2022-06-14 | 复旦大学 | NiS/Cd1-xZnxS goldenrain crystal nanorod composite photocatalyst and preparation method and application thereof |
| CN114713247A (en) * | 2022-03-31 | 2022-07-08 | 福州大学 | Nickel-coated sulfur-manganese-cadmium plasma photocatalyst rich in sulfur vacancy as well as preparation method and application thereof |
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| CN116273060A (en) * | 2023-03-01 | 2023-06-23 | 常州大学 | Preparation method and application of zinc cadmium sulfide and titanium carbide composite photocatalyst |
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