CN110681399A - ZnIn2S4Preparation and application of core-shell type composite photocatalyst - Google Patents
ZnIn2S4Preparation and application of core-shell type composite photocatalyst Download PDFInfo
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- CN110681399A CN110681399A CN201910908454.1A CN201910908454A CN110681399A CN 110681399 A CN110681399 A CN 110681399A CN 201910908454 A CN201910908454 A CN 201910908454A CN 110681399 A CN110681399 A CN 110681399A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 239000011258 core-shell material Substances 0.000 title claims abstract description 41
- 229910002340 LaNiO3 Inorganic materials 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 241000877463 Lanio Species 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 33
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 25
- -1 zinc salt compound Chemical class 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000002135 nanosheet Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006303 photolysis reaction Methods 0.000 claims description 24
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 20
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 20
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 20
- PSCMQHVBLHHWTO-UHFFFAOYSA-K Indium trichloride Inorganic materials Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 13
- 239000011592 zinc chloride Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- 239000003054 catalyst Substances 0.000 abstract description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 9
- 239000004471 Glycine Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- 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—
-
- B01J35/39—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a composite photocatalyst, and in particular relates to ZnIn2S4A base composite photocatalyst and a preparation method and application thereof. ZnIn2S4A base composite photocatalyst consisting essentially of ZnIn2S4Nano sheet loaded LaNiO3LaNiO formed on the surface of the nano-cube3@ZnIn2S4A core-shell type composite photocatalyst. The preparation method comprises the following steps: mixing LaNiO3Dispersing the nanocubes in deionized water, mixing the nanocubes with a zinc salt compound, an indium salt compound and a sulfur-containing compound, carrying out condensation-reflux reaction, collecting precipitates, washing and drying to obtain powder, namely LaNiO3@ZnIn2S4A core-shell type composite photocatalyst. LaNiO of the invention3@ZnIn2S4The core-shell composite photocatalyst can improve the efficiency of photolyzing water to produce hydrogen, and the stability of the catalyst is enhanced.
Description
Technical Field
The invention relates to a composite photocatalyst, and in particular relates to ZnIn2S4A base composite photocatalyst and a preparation method and application thereof.
Background
With the development of modern society, energy crisis and environmental pollution have become important factors influencing the development of human society. H2Has been increasingly gaining attention as a clean energy source. The first report of TiO by Fujishima and Honda in 19722The semiconductor photocatalyst is used for catalyzing the photolysis water to produce hydrogen, and the reaction of the photolysis water to produce hydrogen is attracted by wide attention. But due to TiO2The forbidden band width of the photocatalyst reaches 3.2eV, and the hydrogen production reaction by photolysis is difficult to carry out by utilizing visible light in solar energy, so that the development of a novel visible light response photocatalyst for photolysis hydrogen production is of great significance.
Compared with TiO2The metal sulfide has narrower forbidden bandwidth and lower conduction band potential, and can effectively utilize visible light to carry out the hydrogen production reaction by photolysis. And among the numerous metal sulfides, ZnIn2S4Due to low toxicity, low cost and suitable forbidden bandwidth, a great deal of research has been conducted on photolytic production of hydrogen. However, at present, ZnIn2S4The application of photolysis of water to produce hydrogen is still limited, which is mainly caused by low catalytic efficiency and unstable property. Therefore, the efficiency of photolyzing the water to produce hydrogen is further improved, and the ZnIn is improved2S4The stability of (A) is of great significance.
The method for synthesizing the composite photocatalyst by constructing the heterostructure is an effective way for improving the photocatalytic reaction performance of the semiconductor photocatalyst. For conventional ZnIn2S4The base composite photocatalyst can effectively improve the catalytic reaction efficiency of the common heterostructure, but can not inhibit ZnIn2S4The stability of the catalyst is still not improved. This is mainly due to the conventional ZnIn2S4In the base composite photocatalyst, photoproduction holes are accumulated in ZnIn2S4At the valence band position of (2), the photogenerated holes oxidize ZnIn2S4Crystal lattice S in (1)2-Atoms, resulting in a decrease in the stability of the catalyst.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides LaNiO with high hydrolytic reaction activity and high stability3@ZnIn2S4A core-shell type composite photocatalyst;
correspondingly, the invention also provides a preparation method of the composite photocatalyst, which is simple and feasible and has mild reaction conditions.
Correspondingly, the invention also provides application of the composite photocatalyst in catalyzing the photolysis of water to produce hydrogen.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
ZnIn2S4A core-shell composite photocatalyst which is mainly ZnIn2S4Nano sheet loaded LaNiO3LaNiO formed on the surface of the nano-cube3@ZnIn2S4A core-shell type composite photocatalyst.
The invention provides the LaNiO3@ZnIn2S4The preparation method of the core-shell type composite photocatalyst comprises the following steps of:
S1LaNiO3solution preparation: mixing LaNiO3Dispersing the nanocubes in deionized water, and adjusting the pH value to 1.5-3 to obtain LaNiO3Suspending the solution;
s2 LaNiO3Mixing the suspension solution with a zinc salt compound, an indium salt compound and a sulfur-containing compound to obtain a mixed solution;
s3 condensing and refluxing the mixed solution, collecting the precipitate, washing and drying to obtain light yellow powder, namely LaNiO3@ZnIn2S4A core-shell type composite photocatalyst.
In a preferable embodiment of the preparation method of the present invention, in step S2, the mixed solution is stirred under ultrasonic waves for 1-2 hours.
According to the preferable scheme of the preparation method, in the step S3, the temperature in the condensation-reflux process is 80-160 ℃.
In the preferable scheme of the preparation method, the zinc salt compound is ZnCl2The indium salt compound is InCl3The sulfur-containing compound is thioacetamide.
The invention provides application of the composite photocatalyst in any scheme in catalyzing hydrogen production reaction through photolysis.
The principle of the invention is as follows:
the invention provides a novel semiconductor inorganic perovskite material LaNiO3And ZnIn2S4A direct Z-scheme heterostructure is constructed, which not only improves ZnIn2S4The photocatalytic reaction efficiency of the base composite photocatalyst is improved, and the stability of the catalyst is improved. Wherein, LaNiO3Due to its unique electronic structure and excellent stability, much research has been conducted in the fields of fuel cells, methane reforming and photocatalysis, among which LaNiO3The forbidden band width of the material is 1.9eV, and the conduction band position and the valence band position are respectively positioned at 0.21 eV and 2.21 eV.
Because LaNiO3And ZnIn2S4Appropriate positions of conduction band and valence band, and the combination of them to generate LaNiO3/ZnIn2S4The composite photocatalyst can form a direct Z-scheme heterostructure. In direct Z-scheme heterostructure, LaNiO3Excited electrons in the conduction band can interact with ZnIn2S4Holes in the valence band are combined, and simultaneously, excited electrons and holes are respectively accumulated in ZnIn2S4And LaNiO3The position of the conduction band and the valence band can effectively reduce the recombination probability of photo-generated electrons and holes, effectively promote the migration of photo-generated carriers, improve the photocatalytic reaction efficiency and simultaneously inhibit the crystal lattice S2-Improving the stability of the catalyst, and improving the stability of the catalyst to ZnIn2S4The construction of the base composite photocatalyst is importantThe significance of (1).
(III) advantageous effects
The invention has the beneficial effects that:
1. LaNiO of the invention3@ZnIn2S4The core-shell structure can effectively increase LaNiO3And ZnIn2S4The contact area is beneficial to the transfer of photogenerated electrons and holes between the two, thereby improving the efficiency of the photogenerated water by photolysis.
2. LaNiO of the invention3@ZnIn2S4The construction of the direct Z-scheme heterostructure in the composite photocatalyst is different from the traditional heterostructure, and can effectively inhibit ZnIn2S4The light corrosion phenomenon of the catalyst can be improved, and the stability of the catalyst can be improved.
3. LaNiO of the invention3@ZnIn2S4The preparation method uses common cheap and easily-obtained raw materials as the indium source, the zinc source and the sulfur source, and the raw materials are cheap and easily-obtained and have controllable cost.
4. LaNiO of the invention3@ZnIn2S4The synthesis method is simple and easy to implement, mild in reaction conditions, good in repeatability, considerable in yield and wide in application prospect.
Drawings
FIG. 1 shows LaNiO obtained by the present invention3@ZnIn2S4And LaNiO3、ZnIn2S4XRD pattern of (a);
FIG. 2 shows LaNiO3SEM picture of (1);
FIG. 3 shows the LaNiO obtained by the present invention3@ZnIn2S4SEM picture of (1);
FIG. 4 shows LaNiO obtained by the present invention3@ZnIn2S4And LaNiO3、ZnIn2S4、Pt/ZnIn2S4A comparison graph of the change of the hydrogen amount of the photolyzed water with time;
FIG. 5 shows the LaNiO obtained by the present invention3@ZnIn2S4And ZnIn2S4A comparison graph of hydrogen production in each round of the photolytic hydrogen production cyclic reaction;
FIG. 6 shows ZnIn2S4In circulation ofXRD contrast patterns before and after the ring;
FIG. 7 shows LaNiO obtained by the present invention3@ZnIn2S4XRD patterns before and after cycling.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention by way of specific embodiments thereof.
ZnIn2S4A core-shell composite photocatalyst which is mainly ZnIn2S4Nano sheet loaded LaNiO3LaNiO formed on the surface of the nano-cube3@ZnIn2S4A core-shell type composite photocatalyst.
LaNiO3@ZnIn2S4The core-shell structure can effectively increase LaNiO3And ZnIn2S4The contact area is beneficial to the transfer of photogenerated electrons and holes between the two, and the contact area is particularly applied to the reaction of catalyzing the photolysis of water to generate hydrogen, so that the efficiency of photolysis of water to generate hydrogen can be improved. Meanwhile, the construction of a direct Z mechanism can effectively inhibit ZnIn2S4The light corrosion phenomenon of the catalyst can be improved, and the stability of the catalyst can be improved.
LaNiO3@ZnIn2S4The preparation method of the composite photocatalyst with the core-shell structure is not limited to the following method, and specifically comprises the following steps which are sequentially carried out:
S1LaNiO3solution preparation: mixing LaNiO3Dispersing the nanocubes in deionized water, and adjusting the pH value to 1.5-3 to obtain LaNiO3Suspending the solution; LaNiO3The ratio of the nanocubes to the deionized water is 50-150 mg: 50-150 mL.
S2 LaNiO3Mixing the suspension solution with a zinc salt compound, an indium salt compound and a sulfur-containing compound to obtain a mixed solution;
s3 condensing and refluxing the mixed solution, collecting the precipitate, washing and drying to obtain light yellow powder, namely LaNiO3@ZnIn2S4A core-shell type composite photocatalyst.
In step S2, the mixed solution is stirred for 1-2 hours under ultrasonic wave.
Wherein, in the step S3, the temperature in the condensation-reflux process is 80-160 ℃.
Wherein the zinc salt compound is ZnCl2The indium salt compound is InCl3The sulfur-containing compound is thioacetamide. The zinc salt compound may also be Zn (NO)3)2The indium salt compound is In (NO)3)3。
Wherein, LaNiO3The preparation method of the nanocubes is but not limited to the following steps:
0.4 to 0.5 part by mass of La (NO)3)3·6H2O, 0.2 to 0.4 parts by weight of Ni (NO)3)2·6H2Dissolving O, 0.2-0.4 part by weight of polyvinylpyrrolidone and 0.2-0.4 part by weight of glycine in 50-90 ml of deionized water, and adjusting the pH of the solution to 7.5-7.9 by using ammonia water. And transferring the solution into a reaction kettle, and reacting for 10-14 h at 160-190 ℃. Filtering and drying the obtained product by using deionized water and ethanol solution, and calcining for 1-3 h at 600-700 ℃ to obtain LaNiO3A nanocube.
LaNiO3@ZnIn2S4The application of the core-shell composite photocatalyst in catalyzing the photolysis of water to produce hydrogen comprises the following steps:
adding the obtained composite photocatalyst into deionized water to obtain a composite photocatalyst solution with the weight concentration of 20-40%, adding Triethanolamine (TEOA) with the volume of 5-15% of that of the composite photocatalyst solution as a cavity sacrificial agent, placing the cavity sacrificial agent on a water photolysis device, adding a 420nm cut-off filter with a xenon lamp as a light source, performing a water photolysis reaction at the temperature of 5 ℃, and vacuumizing the system.
Further, the weight concentration of the composite photocatalyst in the composite photocatalyst solution can be 20%, 40%, 28%, 30%, 25%, 33%, and the corresponding added triethanolamine is 5%, 10%, 13%, and 15% of the volume of the composite photocatalyst solution.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
A composite photocatalyst is mainly ZnIn2S4Nano sheet loaded LaNiO3LaNiO formed on the surface of the nano-cube3@ZnIn2S4A core-shell type composite photocatalyst.
Example 2
LaNiO3@ZnIn2S4The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO3preparation of nanocubes
0.5 part by mass of La (NO)3)3·6H2O, 0.4 parts by weight of Ni (NO)3)2·6H2O, 0.4 parts by weight of polyvinylpyrrolidone and 0.4 parts by weight of glycine were dissolved in 90ml of deionized water, and the pH of the solution was adjusted to 7.9 with ammonia water. The solution is transferred to a reaction kettle and reacted for 14 hours at 190 ℃. The obtained product is filtered and dried by deionized water and ethanol solution, and is calcined for 3 hours at 700 ℃ to obtain LaNiO3A nanocube;
S2LaNiO3solution preparation: 50mg of LaNiO is added3Dispersing the nanocubes in deionized water, and adjusting the pH value to 1.5 to obtain LaNiO3Suspending the solution;
s3 LaNiO3Suspension solution with ZnCl2、InCl3Mixing with thioacetamide to obtain a mixed solution, and stirring for 1h under ultrasonic waves; wherein LaNiO used in step S13Cube and ZnCl2、InCl3The mass ratio of thioacetamide powder to thioacetamide powder was 0.15: 1: 2: 4.
S4 subjecting the mixed solution to condensation-reflux reaction at 80 deg.C, collecting reaction precipitate, washing with deionized water by centrifugation, and drying at 50 deg.C to obtain light yellow powder3@ZnIn2S4A core-shell type composite photocatalyst.
Example 3
LaNiO3@ZnIn2S4The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO3preparation of nanocubes
0.433g of La (NO)3)3·6H2O, 0.290g of Ni (NO)3)2·6H2O, 0.30g polyvinylpyrrolidone and 0.375g glycine were dissolved in 70ml deionized water and the solution pH was adjusted to 7.7 with ammonia. The solution is transferred to a reaction kettle and reacted for 12 hours at 180 ℃. The obtained product is filtered and dried by deionized water and ethanol solution, and calcined for 2 hours at 650 ℃ to obtain LaNiO3A nanocube.
S2LaNiO3Suspension preparation: 100mg of LaNiO is added3Dispersing the nanocubes in 100ml of deionized water, and adjusting the pH of the solution to 2 by using HCl to obtain LaNiO3Suspending the solution;
s3 mixing the LaNiO3Adding ZnCl into the suspension2，InCl3And thioacetamide, and ultrasonically stirring for 2 hours at normal temperature to obtain a mixed solution; wherein LaNiO used in step S13Cube and ZnCl2、InCl3The mass ratio of thioacetamide powder to thioacetamide powder was 0.15: 1: 2: 4.
S4 transferring the mixed solution to a round-bottom flask, reacting for 2h by a condensation-reflux method at 100 ℃, collecting reaction precipitates after the reaction is stopped, washing by deionized water in a suction filtration mode, and drying at 60 ℃ to obtain light yellow powder, namely LaNiO3@ZnIn2S4A core-shell type composite photocatalyst. LaNiO prepared by the above reaction3@ZnIn2S4The core-shell type composite photocatalyst can effectively promote the efficiency of hydrogen production reaction by photolysis, and improve the stability of the catalyst. But the material is not limited to applications in the field of photolytic production of hydrogen.
Example 4
LaNiO3@ZnIn2S4The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO3preparation of nanocubes
0.4 part by mass of La (NO)3)3·6H2O、0.2 parts by weight of Ni (NO)3)2·6H2O, 0.2 parts by weight of polyvinylpyrrolidone and 0.2 parts by weight of glycine were dissolved in 50ml of deionized water, and the pH of the solution was adjusted to 7.5 with ammonia water. The solution is transferred to a reaction kettle and reacted for 10 hours at 160 ℃. The obtained product is filtered and dried by deionized water and ethanol solution, and is calcined for 1h at 600 ℃ to obtain LaNiO3A nanocube;
S2LaNiO3solution preparation: 150mgLaNiO is added3Dispersing the nanocubes in deionized water, and adjusting the pH value to 3 to obtain LaNiO3Suspending the solution;
s3 LaNiO3Suspension solution with Zn (NO)3)2、InCl3Mixing with thioacetamide to obtain a mixed solution, and stirring for 2 hours under ultrasonic waves; wherein LaNiO used in step S13Cube and Zn (NO)3)2、InCl3The mass ratio of thioacetamide powder to thioacetamide powder was 0.15: 1: 2: 4.
S4 subjecting the mixed solution to condensation-reflux reaction at 160 deg.C, collecting reaction precipitate, washing with deionized water by centrifugation, and drying at 70 deg.C to obtain light yellow powder3@ZnIn2S4A core-shell type composite photocatalyst.
Example 5
LaNiO3@ZnIn2S4The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO3preparation of nanocubes
0.5 part by mass of La (NO)3)3·6H2O, 0.4 parts by weight of Ni (NO)3)2·6H2O, 0.2-0.4 part by weight of polyvinylpyrrolidone and 0.4 part by weight of glycine are dissolved in 90ml of deionized water, and the pH of the solution is adjusted to 7.9 by using ammonia water. The solution is transferred to a reaction kettle and reacted for 14 hours at 190 ℃. The obtained product is filtered and dried by deionized water and ethanol solution, and is calcined for 3 hours at 700 ℃ to obtain LaNiO3A nanocube;
S2LaNiO3solution preparation: 142mgLaNiO3Dispersing the nanocubes in deionized water, and adjusting the pH value to 2.3 to obtain LaNiO3Suspending the solution;
s3 LaNiO3Suspension solution with ZnCl2、In(NO3)3Mixing with thioacetamide to obtain a mixed solution, and stirring for 1h under ultrasonic waves; wherein LaNiO used in step S13Cube and ZnCl2、In(NO3)3The mass ratio of thioacetamide powder to thioacetamide powder was 0.15: 1: 2: 4.
S4 subjecting the mixed solution to condensation-reflux reaction at 156 ℃, collecting reaction precipitate, washing with deionized water by centrifugation, and drying at 60 ℃ to obtain LaNiO as light yellow powder3@ZnIn2S4The powder of (4), namely the composite photocatalyst.
Example 6
LaNiO3@ZnIn2S4The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO3preparation of nanocubes
0.428 part by mass of La (NO)3)3·6H2O, 0.269 part by weight of Ni (NO)3)2·6H2O, 0.298 parts by weight of polyvinylpyrrolidone and 0.3 parts by weight of glycine are dissolved in 50-90 ml of deionized water, and the pH of the solution is adjusted to 7.6 by using ammonia water. The solution is transferred to a reaction kettle and reacted for 13 hours at 172 ℃. The obtained product is filtered and dried by deionized water and ethanol solution, and is calcined for 1.5h at 665 ℃ to obtain LaNiO3A nanocube;
S2LaNiO3solution preparation: mixing 75mgLaNiO3Dispersing the nanocubes in deionized water, and adjusting the pH value to 1.7 to obtain LaNiO3Suspending the solution;
s3 LaNiO3Solution with ZnCl2、InCl3Mixing with thioacetamide to obtain a mixed solution, and stirring for 1.8h under ultrasonic waves; wherein LaNiO used in step S13Cube and ZnCl2、InCl3And thioacetamide powderThe ratio of the amounts is 0.15: 1: 2: 4.
S4 subjecting the mixed solution to condensation-reflux reaction at 120 deg.C, collecting the reaction precipitate, washing with deionized water by centrifugation, and drying at 50 deg.C to obtain light yellow powder3@ZnIn2S4A core-shell type composite photocatalyst.
Example 7
LaNiO3@ZnIn2S4The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO3preparation of nanocubes
0.5 part by mass of La (NO)3)3·6H2O, 0.3 parts by weight of Ni (NO)3)2·6H2O, 0.2-0.4 part by weight of polyvinylpyrrolidone and 0.2 part by weight of glycine are dissolved in 90ml of deionized water, and the pH of the solution is adjusted to 7.7 by using ammonia water. The solution is transferred to a reaction kettle and reacted for 14 hours at 165 ℃. The obtained product is filtered and dried by deionized water and ethanol solution, and is calcined for 1h at 650 ℃ to obtain LaNiO3A nanocube;
S2LaNiO3solution preparation: 60mg of LaNiO is added3Dispersing the nanocubes in deionized water, and adjusting the pH value to 2.8 to obtain LaNiO3Suspending the solution;
s3 LaNiO3Solution with ZnCl2、InCl3Mixing with thioacetamide to obtain a mixed solution, and stirring for 1.4h under ultrasonic waves; wherein LaNiO used in step S13Cube and ZnCl2、InCl3The mass ratio of thioacetamide powder to thioacetamide powder was 0.15: 1: 2: 4.
S4 subjecting the mixed solution to condensation-reflux reaction at 90 deg.C, collecting the reaction precipitate, washing with deionized water by centrifugation, and drying at 70 deg.C to obtain light yellow powder3@ZnIn2S4A core-shell type composite photocatalyst.
Example 8
LaNiO obtained in example 1 was added3@ZnIn2S4Powder and ZnIn2S4Respectively obtaining XRD patterns shown in figure 1 through XRD detection; as is clear from FIG. 1, LaNiO of example 13@ZnIn2S4XRD diffraction peak of powder and hexagonal ZnIn2S4Has a uniform standard diffraction peak (whose JCPDS card number is No.03-065-2023), wherein the diffraction peaks at 21.2 DEG, 27.1 DEG, 47.1 DEG, 52.4 DEG and 55.6 DEG correspond to ZnIn respectively2S4The (006), (102), (112), (116) and (202) crystal planes of (c). However, LaNiO was not found in the XRD pattern3Corresponding diffraction peaks, probably due to LaNiO3Low content of and ZnIn2S4Is caused by the coating of (a).
Example 9
LaNiO obtained in example 23@ZnIn2S4Powder and LaNiO3Scanning by SEM to obtain SEM images shown in FIGS. 3 and 2; LaNiO as shown in FIG. 23Presenting a 1.5 μm cube. As shown in FIG. 3 with ZnIn2S4Introduction of (1), ZnIn2S4The nano sheet is covered on the LaNiO3LaNiO is formed on the surface of the cube3@ZnIn2S4Core-shell structure. The core-shell structure can effectively increase LaNiO3And ZnIn2The contact area between the S4 is favorable for the transfer of photo-generated electrons and holes between the S4 and the S4.
Example 10
LaNiO obtained in example 3 was added3@ZnIn2S4Powder and LaNiO3、Pt/ZnIn2S4、ZnIn2S4The photolytic hydrogen generation reaction was performed, and the results are shown in fig. 4. As can be seen from FIG. 4, when ZnIn is used2S4The catalyst is used for the photolysis hydrogen production reaction, and only 51.9 mu mol H is left in 5H2. With LaNiO3Introduction of H in the same reaction time2The yield reaches 154.0 mu mol, and the activity is improved by 3.0 times. And compared with Pt/ZnIn2S4Catalyst, LaNiO3@ZnIn2S4The hydrogen production activity of the composite photocatalyst is also improved by 1.6 times.This indicates that the LaNiO is associated with3Introduction of (1), LaNiO3@ZnIn2S4The hydrogen production activity of the composite photocatalyst is effectively improved and even better than that of Pt/ZnIn loaded by noble metal elements2S4A catalyst. This is mainly due to the LaNiO3And ZnIn2S4The heterostructure formed between the two can effectively inhibit the recombination of photo-generated electrons and holes, thereby prolonging the service life of the photo-generated electrons and improving the efficiency of photolysis of water to produce hydrogen.
Example 11
LaNiO obtained in example 5 was added3@ZnIn2S4Composite photocatalyst and ZnIn2S4The performance of the catalyst in hydrogen production by photolysis of water in a circulation experiment and XRD spectrograms of the catalyst before and after reaction are respectively measured. FIG. 5 shows that LaNiO was obtained after 4 cycles of cycling3@ZnIn2S4The activity of the composite photocatalyst for photolyzing water to produce hydrogen is reduced by 6.7 percent, and ZnIn2S4The hydrogen activity of the water produced by catalytic photolysis is reduced by 32.7 percent, and LaNiO can be seen3@ZnIn2S4The stability of the composite photocatalyst for photolyzing water to produce hydrogen is effectively improved. It can be seen from XRD patterns before and after the reaction that ZnIn is formed after the cycle reaction as shown in FIG. 62S4A new peak appears in the XRD pattern of the sulfur-containing material, and corresponds to the diffraction peak of the elemental sulfur. As shown in FIG. 7, LaNiO after the cycling reaction3@ZnIn2S4The XRD pattern of the composite photocatalyst is not changed, which shows that LaNiO3Can effectively improve ZnIn2S4The structural stability of (2).
The method for photolyzing water to produce hydrogen, which is disclosed in the embodiments 1-11 of the invention, comprises the following steps:
LaNiO3@ZnIn2S4the hydrogen production by water photolysis of the composite photocatalyst is carried out on a Pofely water photolysis device, and H can be detected by Shimadzu 8A type gas chromatography2The yield of (2).
Adding 20mg of the obtained composite photocatalyst into 70mL of deionized water, adding 10mL of Triethanolamine (TEOA) as a hole sacrificial agent, taking a xenon lamp as a light source, and adding a 420nm cut-offStopping filtering, performing photolysis water reaction on the photolysis water device, vacuumizing the system at 5 deg.C, illuminating the system with visible light with lambda > 420nm, and detecting H in the system every 1H2After 5 hours, the reaction was terminated.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. LaNiO3@ZnIn2S4The core-shell type composite photocatalyst is characterized in that the core-shell type composite photocatalyst is mainly ZnIn2S4Nano sheet loaded LaNiO3LaNiO formed on the surface of the nano-cube3@ZnIn2S4Core-shell structure.
2. The LaNiO of claim 13@ZnIn2S4The preparation method of the core-shell type composite photocatalyst is characterized by comprising the following steps of:
S1LaNiO3solution preparation: mixing LaNiO3Dispersing the nanocubes in deionized water, and adjusting the pH value to 1.5-3 to obtain LaNiO3Suspending the solution;
s2 LaNiO3Mixing the solution with a zinc salt compound, an indium salt compound and a sulfur-containing compound to obtain a mixed solution;
s3 condensing and refluxing the mixed solution, collecting the precipitate, washing and drying to obtain light yellow powder, namely LaNiO3@ZnIn2S4A core-shell type composite photocatalyst.
3. The LaNiO of claim 23@ZnIn2S4The preparation method of the core-shell type composite photocatalyst is characterized by comprising the following steps: in step S2, the mixture is subjected to ultrafiltrationStirring for 1-2 h under sound waves.
4. The LaNiO of claim 23@ZnIn2S4The preparation method of the core-shell type composite photocatalyst is characterized by comprising the following steps: in step S3, the temperature during the condensation-reflux process is 80-160 ℃.
5. The LaNiO of any of claims 2-43@ZnIn2S4The preparation method of the core-shell type composite photocatalyst is characterized by comprising the following steps: the zinc salt compound is ZnCl2The indium salt compound is InCl3The sulfur-containing compound is thioacetamide.
6. The LaNiO of claim 13@ZnIn2S4The application of the core-shell composite photocatalyst in catalyzing the photolysis of water to produce hydrogen.
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