CN115591558A - Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 Preparation method of (1) - Google Patents
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910052724 xenon Inorganic materials 0.000 abstract description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 230000015556 catabolic process Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UFEHSYWUPMDJLU-UHFFFAOYSA-N cadmium(2+) indium(3+) sulfide Chemical compound [S-2].[Cd+2].[In+3] UFEHSYWUPMDJLU-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000010815 organic waste Substances 0.000 description 1
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- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 description 1
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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
- 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
-
- B01J35/39—
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- 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
Abstract
Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 Belonging to the field of inorganic catalytic materials. The method has the advantages of high uniformity, high purity, low-temperature synthesis, low cost and the like, and has excellent controllability on the crystal, the shape and the size of the synthesized photocatalyst. The preparation operation is simple, the required equipment is few, and the safety coefficient of using sodium sulfide as a precursor is higher. Prepared NiTiO 3 /CdIn 2 S 4 The stability is strong, the photocatalytic activity is high, 0.05g of composite photocatalytic hydrogen production material is dispersed in 10v/v% triethanolamine solution under the irradiation of a simulated sunlight xenon lamp, the hydrogen production amount can reach 739.9 mu mol after 3h of illumination, and the hydrogen production rate can reach 4.93 mmol/g ‑1 ·h ‑1 . The inventionThe prepared product can be widely used in the field of photocatalytic hydrogen production.
Description
Technical Field
The invention relates to a composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 Belonging to the technical field of inorganic catalytic materials.
Background
The photocatalysis technology takes inexhaustible solar energy as a reaction driving force and takes cheap and harmless semiconductor materials as a catalytic reaction medium, and is a green, environment-friendly, safe and economic technology. The method can decompose and convert water into clean and efficient hydrogen energy, has great application potential in hydrogen production, is wide in applicability, easily meets the conditions required by photocatalysis, and is expected to solve the problem of resource shortage through the technology.
Conventional photocatalysts, e.g. TiO 2 And ZnO has wide band gap, extremely low utilization rate of visible light and high excitation energy, and thus the application of ZnO in actual production is hindered. And indium cadmium sulfide (CdIn) 2 S 4 ) Belongs to a cubic spinel structure, has a band gap of about 2.1eV, has excellent light absorption performance in a visible light range, has good photocatalytic activity and photochemical stability, and is widely applied to the fields of photocatalytic oxidation degradation of organic pollutants, decomposition of water for hydrogen evolution, reduction of carbon dioxide, bacteriostasis, organic synthesis and the like. The main preparation methods comprise a hot-wall epitaxial growth method, a thermal evaporation technology, a spray pyrolysis method, a hydrothermal (solvent) thermal method and the like. However, the practical application effect and catalytic activity are still limited by the defects of less surface active sites, poorer electron and hole mobility, higher recombination rate of photon-generated carriers, short service life and the like, and are difficult to satisfy. In recent years, a great deal of research has been conducted on CdIn through loading, doping, semiconductor compounding, and the like 2 S 4 The modification is carried out to achieve the aim of improving the photocatalytic performance of the photocatalyst. Among them, the heterojunction is formed by compounding other semiconductor materials to expand the photoresponse range of the photocatalytic material, improve the overall sunlight utilization rate and quantum yield, improve the separation efficiency of photo-generated electron-hole pairs, inhibit the recombination of photo-generated carriers, and effectively improve the photocatalytic activity of the catalyst, which is favored by a large number of researchers. Nickel titanate (NiTiO) 3 ) Belongs to an ilmenite type structure, has a narrow band gap (about 2.2-2.5 eV) and photoresponse characteristic, has high photostability, corrosion resistance and catalytic activity in an aqueous solution, and has excellent photocatalytic performance on hydrogen evolution, harmful substance degradation and hydrocarbon oxidation. The preparation method mainly comprises a precipitation method, a sol-gel method, a liquid-phase coprecipitation method and the like.
At present, research on composite photocatalysts mainly focuses on improving the catalytic activity of the composite photocatalysts. Such as "Journal of Colloid andinterface Science "volume 5/month 615 (2022)" Design of non-volatile metal-free NiTiO at pages 346-356 3 /ZnIn 2 S 4 heterojunction photocatalyst for efficient visible-light-assisted production of H 2 and selective synthesis of 2,5-Bis (hydroxymethyl) furan ″, nickel titanate is prepared by coprecipitation method, and then put into precursors of indium zinc sulfide (zinc chloride, indium chloride and thioacetamide) according to a certain proportion, and NiTiO is formed after precipitation 3 /ZnIn 2 S 4 A composite photocatalyst. The disadvantages of this method are: (1) In the preparation process, a large amount of acid is needed to regulate the pH value to 2.5, the reaction condition is strict, and acid corrosion resistant equipment is needed; (2) The coprecipitation method is used for preparing the composite material, so that the uniformity of the particle size distribution of a sample is difficult to control; (3) The use of thioacetamide, an organic substance, as a sulfur source poses a carcinogenic risk in contact therewith and produces high-concentration organic waste water, which may cause environmental pollution.
Disclosure of Invention
The invention aims at the NiTiO 3 、CdIn 2 S 4 In the preparation process, the problems of high organic matter consumption, poor photocatalytic activity of the compound and the like are solved, and the hydrothermal method for preparing the composite photocatalytic material NiTiO is provided 3 /CdIn 2 S 4 The method improves the activity and stability of the composite photocatalytic material, the preparation process is simple, the period is short, the catalytic activity is high, and the composite photocatalytic hydrogen production material NiTiO of the invention 3 /CdIn 2 S 4 The preparation method comprises the following steps:
(1)NiTiO 3 preparation of
2.9868g of nickel acetate (Ni (Ac) was weighed 2 ·4H 2 O) was dissolved in 72mL of ethylene glycol, stirred for 2h to form a green solution, and then 4.08mL of tetrabutyl titanate (Ti (OC) was added 4 H 9 ) 4 ) After magnetic stirring for 1h, centrifugally washing the precipitate, and drying in an oven at 80 ℃ for 12h to obtain a precursor; at the temperature rising speed of 5 ℃/min, the precursor is placed in a muffle furnace at the temperature of 600 ℃, calcined for 2h and cooled to obtain NiTiO 3 ；
(2) Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 Preparation of
0.2498g cadmium acetate (Cd (Ac) are weighed 2 ·2H 2 O) and 0.5497g indium trichloride (InCl) 3 ·4H 2 O), dissolving the mixture in 30mL of deionized water by mixed ultrasound, and continuing to perform ultrasound for 30min to obtain a solution A; according to NiTiO 3 Weighing NiTiO with the mass ratio of 10-25% in the compound 3 Putting the powder in the solution A, and magnetically stirring for 30min to obtain a suspension B; 1.125g of sodium sulfide (Na) are weighed out 2 S·9H 2 O) dissolving in 30mL of deionized water for 30min by ultrasonic wave to obtain a solution C; slowly dropwise adding the solution C into the suspension B, continuously stirring for 2-3 h, transferring to a 100mL reaction kettle, performing hydrothermal reaction at 200 ℃ for 24h, naturally cooling to room temperature, filtering, respectively centrifugally washing filter cakes with deionized water and absolute ethyl alcohol for 3 times, drying in an oven at 80 ℃ for 12h, taking out, cooling, and grinding into powder by using a quartz mortar to obtain the composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 。
By adopting the technical scheme, the invention mainly has the following effects:
(1) NiTiO prepared by the method of the invention 3 /CdIn 2 S 4 The composite photocatalytic material has higher photocatalytic activity, and 0.05g of the composite photocatalytic material NiTiO is irradiated by a xenon lamp (340-800 nm) simulating sunlight 3 /CdIn 2 S 4 Dispersed in 10v/v% triethanolamine solution, the hydrogen production amount reaches 739.9 mu mol after 3h of illumination, and the hydrogen production rate reaches 4.93 mmol/g -1 ·h -1 。
(2) The invention is prepared by a hydrothermal method, has the advantages of high uniformity, high purity, low-temperature synthesis, low cost and the like, and has excellent controllability on the crystal, the shape and the size of the synthesized photocatalyst. The preparation operation is simple, the required equipment is less, and the safety coefficient of using sodium sulfide as a precursor is higher.
Drawings
FIG. 1 shows NiTiO 3 、CdIn 2 S 4 And NiTiO 3 /CdIn 2 S 4 X-ray diffraction pattern of (a).
FIG. 2 shows NiTiO 3 、CdIn 2 S 4 And NiTiO 3 /CdIn 2 S 4 Is compared with the hydrogen production.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 The preparation method comprises the following specific steps:
(1)NiTiO 3 preparation of
2.9868g of Nickel acetate (Ni (Ac) was weighed 2 ·4H 2 O) was dissolved in 72mL of ethylene glycol, stirred for 2h to form a green solution, and then 4.08mL of tetrabutyl titanate (Ti (OC) was added 4 H 9 ) 4 ) After magnetic stirring for 1h, centrifugally washing the precipitate, and drying in an oven at 80 ℃ for 12h to obtain a precursor; at the temperature rising speed of 5 ℃/min, the precursor is placed in a muffle furnace at the temperature of 600 ℃, calcined for 2h and cooled to obtain NiTiO 3 ；
(2) Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 Preparation of
0.2498g cadmium acetate (Cd (Ac) are weighed 2 ·2H 2 O) and 0.5497g indium trichloride (InCl) 3 ·4H 2 O), dissolving the mixture in 30mL of deionized water by ultrasonic treatment, and continuing ultrasonic treatment for 30min to obtain a solution A; according to NiTiO 3 Weighing NiTiO with the mass ratio of 10% in the compound 3 Putting the powder into the solution A, and magnetically stirring for 30min to obtain a suspension B; 1.125g of sodium sulfide (Na) are weighed out 2 S·9H 2 O) dissolving in 30mL of deionized water for 30min by ultrasonic to obtain a solution C; slowly dropwise adding the solution C into the suspension B, continuously stirring for 2-3 h, transferring to a 100mL reaction kettle, performing hydrothermal reaction at 200 ℃ for 24h, naturally cooling to room temperature, filtering, respectively centrifugally washing filter cakes with deionized water and absolute ethyl alcohol for 3 times, drying in an oven at 80 ℃ for 12h, taking out, cooling, and grinding into powder by using a quartz mortar to obtain the composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 。
Example 2
Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 The preparation method comprises the following specific steps:
(1) Same as in (1) of example 1
(2) Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 Preparation of
0.2498g cadmium acetate (Cd (Ac) are weighed 2 ·2H 2 O) and 0.5497g indium trichloride (InCl) 3 ·4H 2 O), dissolving the mixture in 30mL of deionized water by mixed ultrasound, and continuing to perform ultrasound for 30min to obtain a solution A; according to NiTiO 3 Weighing NiTiO 15 wt% in the composite 3 Putting the powder into the solution A, and magnetically stirring for 30min to obtain a suspension B; 1.125g of sodium sulfide (Na) are weighed out 2 S·9H 2 O) dissolving in 30mL of deionized water for 30min by ultrasonic wave to obtain a solution C; slowly dropwise adding the solution C into the suspension B, continuously stirring for 2-3 h, transferring to a 100mL reaction kettle, performing hydrothermal reaction at 200 ℃ for 24h, naturally cooling to room temperature, filtering, respectively centrifugally washing filter cakes with deionized water and absolute ethyl alcohol for 3 times, drying in an oven at 80 ℃ for 12h, taking out, cooling, and grinding into powder by using a quartz mortar to obtain the composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 。
Example 3
Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 The preparation method comprises the following specific steps:
(1) Same as in (1) of example 1
(2) Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 Preparation of
0.2498g cadmium acetate (Cd (Ac) are weighed 2 ·2H 2 O) and 0.5497g indium trichloride (InCl) 3 ·4H 2 O), dissolving the mixture in 30mL of deionized water by ultrasonic treatment, and continuing ultrasonic treatment for 30min to obtain a solution A; according to NiTiO 3 Weighing NiTiO 20 wt% in the composite 3 Putting the powder into the solution A, and magnetically stirring for 30min to obtain a suspension B; 1.125g of sodium sulfide (Na) are weighed out 2 S·9H 2 O) dissolving in 30mL of deionized water for 30min by ultrasonic to obtain a solution C;slowly dropwise adding the solution C into the suspension B, continuously stirring for 2-3 h, transferring to a 100mL reaction kettle, performing hydrothermal reaction at 200 ℃ for 24h, naturally cooling to room temperature, filtering, respectively centrifugally washing filter cakes with deionized water and absolute ethyl alcohol for 3 times, drying in an oven at 80 ℃ for 12h, taking out, cooling, and grinding into powder by using a quartz mortar to obtain the composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 。
Example 4
Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 The preparation method comprises the following specific steps:
(1) Same as in (1) of example 1
(2) Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 Preparation of
0.2498g cadmium acetate (Cd (Ac) are weighed 2 ·2H 2 O) and 0.5497g indium trichloride (InCl) 3 ·4H 2 O), dissolving the mixture in 30mL of deionized water by ultrasonic treatment, and continuing ultrasonic treatment for 30min to obtain a solution A; according to NiTiO 3 Weighing NiTiO with the mass ratio of 25 percent in the compound 3 Putting the powder into the solution A, and magnetically stirring for 30min to obtain a suspension B; 1.125g of sodium sulfide (Na) are weighed out 2 S·9H 2 O) dissolving in 30mL of deionized water for 30min by ultrasonic wave to obtain a solution C; slowly dropwise adding the solution C into the suspension B, continuously stirring for 2-3 h, transferring to a 100mL reaction kettle, performing hydrothermal reaction at 200 ℃ for 24h, naturally cooling to room temperature, filtering, respectively centrifugally washing filter cakes with deionized water and absolute ethyl alcohol for 3 times, drying in an oven at 80 ℃ for 12h, taking out, cooling, and grinding into powder by using a quartz mortar to obtain the composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 。
Results of the experiment
Composite photocatalytic material NiTiO prepared in example 3 3 /CdIn 2 S 4 The catalytic degradation activity is optimal. For comparison, cdIn was prepared 2 S 4 And (3) sampling. CdIn 2 S 4 The preparation method is that no NiTiO is added in the step (2) of the example 3 3 。
NiTiO 3 The XRD of (A) is shown in figure 1 (a), and obvious diffraction peaks appear at 24.1 degrees, 33.1 degrees, 35.7 degrees, 40.9 degrees, 49.4 degrees, 54 degrees, 62.4 degrees and 64.1 degrees, which is similar to that of NiTiO of the hexagonal system (JCPDS: 33-0960) 3 The (012), (104), (110), (113), (024), (116), (214), and (300) crystal planes of (a) correspond to each other. CdIn 2 S 4 As shown in FIG. 1 (b), the characteristic diffraction peaks at 27.3 DEG, 45.3 DEG and 52.3 DEG of 2 theta are respectively corresponding to CdIn in of cubic system (JCPDS: 27-0060) 2 S 4 The (311), (511) and (531) crystal planes of (a).
Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 XRD diffraction of the product is shown in FIG. 1 (c), niTiO 3 /CdIn 2 S 4 The diffraction peak of the sample contained not only CdIn 2 S 4 The characteristic diffraction peaks of (311), (511) and (531), and NiTiO can be observed very clearly 3 The characteristic diffraction peaks of (012), (104), (110), (113), (024), (116), (214) and (300) of (a) are also present at the same time, the diffraction peaks are sharp and no impurity peak appears, which indicates that the NiTiO 3 /CdIn 2 S 4 The sample preparation was successful.
In a closed gas circulation system with constant temperature, a 300W xenon lamp is used for simulating sunlight, 0.05g of the prepared composite photocatalytic hydrogen production material is dispersed in 100mL of 10v/v% triethanolamine solution, vacuumizing is performed before light irradiation, and then nitrogen is introduced into a reactor to ensure an oxygen-free environment; and (5) illuminating for 3h, and measuring the hydrogen amount by using a gas chromatograph every half hour. CdIn 2 S 4 、NiTiO 3 And the hydrogen production of the composite material is shown in figure 2. Thus, the NiTiO with the composite mass ratio of 20 percent 3 /CdIn 2 S 4 The hydrogen production performance is optimal, the hydrogen production amount is 739.9 mu mol in 3h, and the hydrogen production rate can reach 4.93 mmol/g -1 ·h -1 Are respectively about CdIn 2 S 4 And NiTiO 3 7.7 times and 814.9 times.
Claims (2)
1. Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 The preparation method comprises the following steps:
(1)NiTiO 3 preparation of
2.9868g of nickel acetate (Ni (Ac) was weighed 2 ·4H 2 O) was dissolved in 72mL of ethylene glycol, stirring was continued for 2h to form a green solution, and then 4.08mL of tetrabutyl titanate (Ti (OC) was added 4 H 9 ) 4 ) After magnetic stirring for 1h, centrifugally washing the precipitate, and drying in an oven at 80 ℃ for 12h to obtain a precursor; at the temperature rise speed of 5 ℃/min, the precursor is placed in a muffle furnace at the temperature of 600 ℃, calcined for 2h and cooled to obtain the NiTiO 3 ；
(2) Composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 Preparation of
0.2498g cadmium acetate (Cd (Ac) are weighed 2 ·2H 2 O) and 0.5497g indium trichloride (InCl) 3 ·4H 2 O), dissolving the mixture in 30mL of deionized water by ultrasonic treatment, and continuing ultrasonic treatment for 30min to obtain a solution A; according to NiTiO 3 Weighing NiTiO with the mass ratio of 10-25% in the compound 3 Putting the powder into the solution A, and magnetically stirring for 30min to obtain a suspension B; 1.125g of sodium sulfide (Na) are weighed out 2 S·9H 2 O) dissolving in 30mL of deionized water for 30min by ultrasonic wave to obtain a solution C; slowly dropwise adding the solution C into the suspension B, continuously stirring for 2-3 h, transferring to a 100mL reaction kettle, performing hydrothermal reaction at 200 ℃ for 24h, naturally cooling to room temperature, filtering, respectively centrifugally washing filter cakes with deionized water and absolute ethyl alcohol for 3 times, drying in an oven at 80 ℃ for 12h, taking out, cooling, and grinding into powder by using a quartz mortar to obtain the composite photocatalytic hydrogen production material NiTiO 3 /CdIn 2 S 4 。
2. The composite photocatalytic hydrogen production material NiTiO as claimed in claim 1 3 /CdIn 2 S 4 The preparation method is characterized by hydrothermal preparation, and realizes the catalytic active component NiTiO 3 And CdIn 2 S 4 The firm combination between them.
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