CN110681399B - ZnIn 2 S 4 Preparation and application of core-shell type composite photocatalyst - Google Patents
ZnIn 2 S 4 Preparation and application of core-shell type composite photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 241000877463 Lanio Species 0.000 claims abstract description 119
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 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 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 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
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 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 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000006303 photolysis reaction Methods 0.000 claims description 20
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 20
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 19
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 19
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 13
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 abstract description 15
- 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
- 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
- 238000000034 method Methods 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 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
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 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
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 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
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 238000005286 illumination Methods 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
- 238000002407 reforming Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 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
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- B01J35/30—
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- B01J35/39—
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- 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
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- 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 ZnIn 2 S 4 A base composite photocatalyst and a preparation method and application thereof. ZnIn 2 S 4 A base composite photocatalyst consisting essentially of ZnIn 2 S 4 Nano sheet loaded LaNiO 3 LaNiO formed on the surface of the nano-cube 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst. The preparation method comprises the following steps: mixing LaNiO 3 Dispersing nanocubes in deionized water, mixing 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 LaNiO 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst. LaNiO of the invention 3 @ZnIn 2 S 4 The core-shell composite photocatalyst can improve the efficiency of photolyzing water to produce hydrogen, and meanwhile, the stability of the catalyst is enhanced.
Description
Technical Field
The invention relates to a composite photocatalyst, and in particular relates to ZnIn 2 S 4 A 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. H 2 Has been increasingly gaining attention as a clean energy source. The first report of TiO by Fujishima and Honda in 1972 2 Photolytic aquaculture of catalystsHydrogen, a reaction for producing hydrogen by photocatalytic decomposition of water with a semiconductor photocatalyst, has received a great deal of attention. But due to TiO 2 The 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 TiO 2 The 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, znIn 2 S 4 Due 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, znIn 2 S 4 The application of photolysis of water to produce hydrogen is still limited, mainly due to low catalytic efficiency and unstable properties. Therefore, the efficiency of photolyzing the water to produce hydrogen is further improved, and the ZnIn is improved 2 S 4 The stability of (A) is of great significance.
The method is an effective way for improving the photocatalytic reaction performance of the semiconductor photocatalyst by constructing a composite photocatalyst synthesized by a heterostructure. For conventional ZnIn 2 S 4 The base composite photocatalyst can effectively improve the catalytic reaction efficiency of the common heterostructure, but can not inhibit ZnIn 2 S 4 The stability of the catalyst is still not improved. This is mainly due to the conventional ZnIn 2 S 4 In the base composite photocatalyst, photoproduction holes are accumulated in ZnIn 2 S 4 At the valence band position of (2), the photogenerated holes oxidize ZnIn 2 S 4 Crystal 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 stability 3 @ZnIn 2 S 4 A 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:
ZnIn 2 S 4 The core-shell composite photocatalyst is mainly ZnIn 2 S 4 Nano sheet loaded LaNiO 3 LaNiO formed on the surface of the nano-cube 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst.
The invention provides the LaNiO 3 @ZnIn 2 S 4 The preparation method of the core-shell type composite photocatalyst comprises the following steps of:
S1LaNiO 3 solution preparation: mixing LaNiO 3 Dispersing the nanocubes in deionized water, and adjusting the pH value to 1.5-3 to obtain LaNiO 3 Suspending the solution;
s2 LaNiO 3 Mixing the suspension solution with a zinc salt compound, an indium salt compound and a sulfur-containing compound to obtain a mixed solution;
s3, after the mixed solution is subjected to condensation-reflux reaction, collecting precipitate, washing and drying to obtain light yellow powder, namely LaNiO 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst.
In the preferable scheme of the preparation method, in the step S2, the mixed solution is stirred for 1-2 hours under ultrasonic wave.
In 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 ZnCl 2 The indium salt compound is InCl 3 The 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 LaNiO 3 And ZnIn 2 S 4 A direct Z-scheme heterostructure is constructed, which not only improves ZnIn 2 S 4 The photocatalytic reaction efficiency of the base composite photocatalyst is improved, and the stability of the catalyst is improved. Wherein, laNiO 3 Due 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 LaNiO 3 The 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 2.21eV.
Because LaNiO 3 And ZnIn 2 S 4 Appropriate positions of conduction band and valence band, and the combination of them to generate LaNiO 3 /ZnIn 2 S 4 The composite photocatalyst can form a direct Z-scheme heterostructure. In direct Z-scheme heterostructure, laNiO 3 Excited electrons in the conduction band can interact with ZnIn 2 S 4 Holes in the valence band are combined, and simultaneously, excited electrons and holes are respectively accumulated in ZnIn 2 S 4 And LaNiO 3 The 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 inhibit crystal lattices S 2- Improving the stability of the catalyst, and improving the stability of the catalyst to ZnIn 2 S 4 The construction of the base composite photocatalyst has important significance.
(III) advantageous effects
The invention has the beneficial effects that:
1. LaNiO of the invention 3 @ZnIn 2 S 4 The core-shell structure can effectively increase LaNiO 3 And ZnIn 2 S 4 The 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 invention 3 @ZnIn 2 S 4 The construction of the direct Z-scheme heterostructure in the composite photocatalyst is different from the traditional heterostructure, and the ZnIn can be effectively inhibited 2 S 4 The stability of the catalyst is improved.
3. LaNiO of the invention 3 @ZnIn 2 S 4 The 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 invention 3 @ZnIn 2 S 4 The 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 invention 3 @ZnIn 2 S 4 And LaNiO 3 、ZnIn 2 S 4 XRD pattern of (a);
FIG. 2 shows LaNiO 3 SEM picture of (g);
FIG. 3 shows LaNiO obtained by the present invention 3 @ZnIn 2 S 4 SEM picture of (g);
FIG. 4 shows LaNiO obtained by the present invention 3 @ZnIn 2 S 4 And LaNiO 3 、ZnIn 2 S 4 、Pt/ZnIn 2 S 4 A comparison graph of the change of the hydrogen amount of the photolyzed water with time;
FIG. 5 shows the LaNiO obtained by the present invention 3 @ZnIn 2 S 4 And ZnIn 2 S 4 A comparison graph of hydrogen production in each round of the photolytic hydrogen production cyclic reaction;
FIG. 6 shows ZnIn 2 S 4 XRD patterns before and after cycling;
FIG. 7 shows LaNiO obtained by the present invention 3 @ZnIn 2 S 4 XRD comparison 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.
ZnIn 2 S 4 A core-shell composite photocatalyst which is mainly ZnIn 2 S 4 Nano sheet loaded LaNiO 3 LaNiO formed on the surface of the nano-cube 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst.
LaNiO 3 @ZnIn 2 S 4 The core-shell structure can effectively increase LaNiO 3 And ZnIn 2 S 4 The 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 ZnIn 2 S 4 The light corrosion phenomenon of the catalyst can be improved, and the stability of the catalyst can be improved.
LaNiO 3 @ZnIn 2 S 4 The 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:
S1LaNiO 3 solution preparation: mixing LaNiO 3 Dispersing the nanocubes in deionized water, and adjusting the pH value to 1.5-3 to obtain LaNiO 3 Suspending the solution; laNiO 3 The ratio of the nanocubes to the deionized water is 50-150 mg: 50-150 mL.
S2 LaNiO 3 Mixing the suspension solution with a zinc salt compound, an indium salt compound and a sulfur-containing compound to obtain a mixed solution;
s3, after the mixed solution is subjected to condensation-reflux reaction, collecting precipitate, and washing and drying to obtain light yellow powder, namely LaNiO 3 @ZnIn 2 S 4 A 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 ZnCl 2 The indium salt compound is InCl 3 The sulfur-containing compound is thioacetamide. The zinc salt compound may also be Zn (NO) 3 ) 2 The indium salt compound is In (NO) 3 ) 3 。
Wherein, laNiO 3 The preparation method of the nanocube is, but not limited to, the following steps:
0.4 to 0.5 part by mass of La (N)O 3 ) 3 ·6H 2 O, 0.2-0.4 weight part of Ni (NO) 3 ) 2 ·6H 2 Dissolving 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. The solution is transferred into a reaction kettle and reacts for 10 to 14 hours at the temperature of between 160 and 190 ℃. The obtained product is filtered and dried by deionized water and ethanol solution, and is calcined for 1 to 3 hours at the temperature of between 600 and 700 ℃ to obtain LaNiO 3 A nanocube.
LaNiO 3 @ZnIn 2 S 4 The 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 composite photocatalyst solution on a photolysis water splitting device, taking a xenon lamp as a light source, adding a 420nm cut-off filter, carrying out photolysis water 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 which is mainly ZnIn 2 S 4 Nano sheet loaded LaNiO 3 LaNiO formed on the surface of the nano-cube 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst.
Example 2
LaNiO 3 @ZnIn 2 S 4 The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO 3 preparation of nanocubes
0.5 part by mass of La (NO) 3 ) 3 ·6H 2 O, 0.4 parts by weight of Ni (NO) 3 ) 2 ·6H 2 O, 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 LaNiO 3 A nanocube;
S2LaNiO 3 solution preparation: 50mg of LaNiO was added 3 Dispersing the nanocubes in deionized water, and adjusting the pH value to 1.5 to obtain LaNiO 3 Suspending the solution;
s3 LaNiO 3 Suspension solution with ZnCl 2 、InCl 3 Mixing with thioacetamide to obtain a mixed solution, and stirring for 1h under ultrasonic waves; wherein, laNiO used in step S1 3 Cube and ZnCl 2 、InCl 3 And thioacetamide powder in a mass ratio of 0.15: 1: 2: 4.
S4, carrying out condensation-reflux reaction on the mixed solution at 80 ℃, collecting reaction precipitate, washing by using deionized water in a centrifugal mode, and drying at 50 ℃ to obtain light yellow powder, namely LaNiO 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst.
Example 3
LaNiO 3 @ZnIn 2 S 4 The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO 3 preparation of nanocubes
0.433g of La (NO) 3 ) 3 ·6H 2 O, 0.290g of Ni (NO) 3 ) 2 ·6H 2 O, 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 LaNiO 3 A nanocube.
S2LaNiO 3 Preparing a suspension: 100mg of LaNiO was added 3 Dispersing the nanocubes in 100ml of deionized water, and adjusting the pH of the solution to 2 by using HCl to obtain LaNiO 3 Suspending the solution;
s3, mixing the obtained LaNiO 3 Adding ZnCl into the suspension 2 ，InCl 3 And thioacetamide, and ultrasonically stirring for 2 hours at normal temperature to obtain a mixed solution; wherein, laNiO used in step S1 3 Cube and ZnCl 2 、 InCl 3 The 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 2 hours by a condensation-reflux method, setting the temperature 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 LaNiO 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst. LaNiO prepared by the above reaction 3 @ZnIn 2 S 4 The 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
LaNiO 3 @ZnIn 2 S 4 The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO 3 preparation of nanocubes
0.4 part by mass of La (NO) 3 ) 3 ·6H 2 O, 0.2 parts by weight of Ni (NO) 3 ) 2 ·6H 2 O, 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 LaNiO 3 A nanocube;
S2LaNiO 3 solution preparation: 150mgLaNiO is added 3 Dispersing the nanocubes in deionized water, and adjusting the pH value to 3 to obtain LaNiO 3 Suspending the solution;
s3 willLaNiO 3 Suspension solution with Zn (NO) 3 ) 2 、InCl 3 Mixing with thioacetamide to obtain a mixed solution, and stirring for 2 hours under ultrasonic waves; wherein, laNiO used in step S1 3 Cubic with Zn (NO) 3 ) 2 、InCl 3 The mass ratio of thioacetamide powder to thioacetamide powder was 0.15: 1: 2: 4.
S4, carrying out condensation-reflux reaction on the mixed solution at 160 ℃, collecting reaction precipitates, washing the reaction precipitates by using deionized water in a centrifugal mode, and drying the reaction precipitates at 70 ℃ to obtain light yellow powder, namely LaNiO 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst.
Example 5
LaNiO 3 @ZnIn 2 S 4 The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO 3 preparation of nanocubes
0.5 part by mass of La (NO) 3 ) 3 ·6H 2 O, 0.4 parts by weight of Ni (NO) 3 ) 2 ·6H 2 O, 0.2 to 0.4 part by weight of polyvinylpyrrolidone and 0.4 part 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 LaNiO 3 A nanocube;
S2LaNiO 3 solution preparation: 142mgLaNiO is added 3 Dispersing the nanocubes in deionized water, and adjusting the pH value to 2.3 to obtain LaNiO 3 Suspending the solution;
s3 LaNiO 3 Suspension solution with ZnCl 2 、In(NO 3 ) 3 Mixing with thioacetamide to obtain a mixed solution, and stirring for 1h under ultrasonic waves; wherein, laNiO used in step S1 3 Cube and ZnCl 2 、 In(NO 3 ) 3 The mass ratio of thioacetamide powder to thioacetamide powder was 0.15: 1: 2: 4.
S4, after the mixed solution is subjected to condensation-reflux reaction at 156 ℃, collecting reaction precipitate, and separatingIn a heart mode, deionized water is adopted for washing, and the light yellow powder obtained by drying at 60 ℃ is LaNiO 3 @ZnIn 2 S 4 The powder of (4), namely the composite photocatalyst.
Example 6
LaNiO 3 @ZnIn 2 S 4 The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO 3 preparation of nanocubes
0.428 part by mass of La (NO) 3 ) 3 ·6H 2 O, 0.269 part by weight of Ni (NO) 3 ) 2 ·6H 2 O, 0.298 parts by weight of polyvinylpyrrolidone and 0.3 parts by weight of glycine were dissolved in 50 to 90ml of deionized water, and the pH of the solution was adjusted to 7.6 with 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 LaNiO 3 A nanocube;
S2LaNiO 3 solution preparation: mixing 75mgLaNiO 3 Dispersing the nanocubes in deionized water, and adjusting the pH value to 1.7 to obtain LaNiO 3 Suspending the solution;
s3 LaNiO 3 Solution with ZnCl 2 、InCl 3 Mixing with thioacetamide to obtain a mixed solution, and stirring for 1.8h under ultrasonic waves; wherein, laNiO used in step S1 3 Cube and ZnCl 2 、InCl 3 And thioacetamide powder in a mass ratio of 0.15: 1: 2: 4.
S4, carrying out condensation-reflux reaction on the mixed solution at 120 ℃, collecting reaction precipitate, washing by using deionized water in a centrifugal mode, and drying at 50 ℃ to obtain light yellow powder, namely LaNiO 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst.
Example 7
LaNiO 3 @ZnIn 2 S 4 The preparation method of the core-shell type composite photocatalyst comprises the following steps:
S1LaNiO 3 preparation of nanocubes
0.5 part by mass of La (NO) 3 ) 3 ·6H 2 O, 0.3 parts by weight of Ni (NO) 3 ) 2 ·6H 2 O, 0.2 to 0.4 part by weight of polyvinylpyrrolidone and 0.2 part by weight of glycine were dissolved in 90ml of deionized water, and the pH of the solution was adjusted to 7.7 with 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 LaNiO 3 A nanocube;
S2LaNiO 3 solution preparation: 60mg of LaNiO was added 3 Dispersing the nanocubes in deionized water, and adjusting the pH value to 2.8 to obtain LaNiO 3 Suspending the solution;
s3 LaNiO 3 Solution with ZnCl 2 、InCl 3 Mixing with thioacetamide to obtain a mixed solution, and stirring for 1.4 hours under ultrasonic waves; wherein, laNiO used in step S1 3 Cube and ZnCl 2 、InCl 3 The mass ratio of thioacetamide powder to thioacetamide powder was 0.15: 1: 2: 4.
S4, carrying out condensation-reflux reaction on the mixed solution at 90 ℃, collecting reaction precipitate, washing by using deionized water in a centrifugal mode, and drying at 70 ℃ to obtain light yellow powder, namely LaNiO 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst.
Example 8
LaNiO obtained in example 1 was added 3 @ZnIn 2 S 4 Powder and ZnIn 2 S 4 Respectively obtaining XRD patterns shown in figure 1 through XRD detection; as is clear from FIG. 1, laNiO of example 1 3 @ZnIn 2 S 4 XRD diffraction peak of powder and hexagonal ZnIn 2 S 4 Has a uniform standard diffraction peak (JCPDS card No. 03-065-2023), wherein diffraction peaks at 21.2 DEG, 27.1 DEG, 47.1 DEG, 52.4 DEG and 55.6 DEG correspond to ZnIn 2 S 4 The (006), (102), (112), (116), and (202) planes of (c). However, laNiO was not found in the XRD pattern 3 Corresponding diffraction peaks, probably due to LaNiO 3 Low content of and ZnIn 2 S 4 Is caused by the coating of (a).
Example 9
LaNiO obtained in example 2 3 @ZnIn 2 S 4 Powder and LaNiO 3 Scanning by SEM to obtain SEM images shown in FIGS. 3 and 2; laNiO as shown in FIG. 2 3 Presenting a 1.5 μm cube. As shown in FIG. 3 with ZnIn 2 S 4 Introduction of (1), znIn 2 S 4 The nano sheet is covered on the LaNiO 3 LaNiO is formed on the surface of the cube 3 @ZnIn 2 S 4 Core-shell structure. The core-shell structure can effectively increase LaNiO 3 And ZnIn 2 And the contact area between the S4 is favorable for the transfer of photogenerated electrons and holes between the S4 and the S.
Example 10
LaNiO obtained in example 3 was added 3 @ZnIn 2 S 4 Powder and LaNiO 3 、Pt/ZnIn 2 S 4 、ZnIn 2 S 4 The photolytic hydrogen generation reaction was performed, and the results are shown in fig. 4. As can be seen from FIG. 4, when ZnIn is used 2 S 4 The catalyst is used for the hydrogen production reaction of photolysis water, and only 51.9 mu mol H is left in the reaction time of 5H 2 . With LaNiO 3 Introduction of H in the same reaction time 2 The yield reaches 154.0 mu mol, and the activity is improved by 3.0 times. And compared with Pt/ZnIn 2 S 4 Catalyst, laNiO 3 @ZnIn 2 S 4 The hydrogen production activity of the composite photocatalyst is also improved by 1.6 times. This indicates that the LaNiO is associated with 3 Introduction of (1), laNiO 3 @ZnIn 2 S 4 The hydrogen production activity of the composite photocatalyst is effectively improved and even better than that of Pt/ZnIn loaded by noble metal elements 2 S 4 A catalyst. This is mainly due to the LaNiO 3 And ZnIn 2 S 4 The 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 added 3 @ZnIn 2 S 4 Composite photocatalyst and ZnIn 2 S 4 The 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 cycling 3 @ZnIn 2 S 4 The activity of the composite photocatalyst for photolyzing water to produce hydrogen is reduced by 6.7 percent, and ZnIn 2 S 4 The hydrogen activity of the water produced by catalytic photolysis is reduced by 32.7 percent, and LaNiO can be seen 3 @ZnIn 2 S 4 The 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. 6 2 S 4 A new peak appears in the XRD pattern of (A), which corresponds to the diffraction peak of elemental sulfur. As shown in FIG. 7, laNiO after the cycling reaction 3 @ZnIn 2 S 4 The XRD pattern of the composite photocatalyst is not changed, which shows that LaNiO 3 Can effectively improve ZnIn 2 S 4 The 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:
LaNiO 3 @ZnIn 2 S 4 the 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 chromatography 2 The yield of (2).
Adding 20mg of the obtained composite photocatalyst into 70mL of deionized water, adding 10mL of Triethanolamine (TEOA) as a cavity sacrificial agent, taking a xenon lamp as a light source, adding a 420nm cut-off filter, performing a photolytic water splitting reaction on a photolytic water splitting device, vacuumizing the system, performing illumination on the system by using visible light with lambda being more than 420nm, and detecting H in the system every 1 hour 2 After 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 think of the changes or substitutions within the technical scope of the present invention, and shall cover 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 (2)
1. LaNiO 3 @ZnIn 2 S 4 The core-shell type composite photocatalyst is characterized in that the core-shell type composite photocatalyst is mainly ZnIn 2 S 4 Nano sheet loaded LaNiO 3 LaNiO formed on the surface of the nano-cube 3 @ZnIn 2 S 4 A core-shell structure;
the LaNiO 3 @ZnIn 2 S 4 The preparation method of the core-shell type composite photocatalyst comprises the following steps of:
S1LaNiO 3 solution preparation: mixing LaNiO 3 Dispersing the nanocubes in deionized water, and adjusting the pH value to be 1.5-3 to obtain LaNiO 3 Suspending the solution;
s2 LaNiO 3 Mixing the solution with a zinc salt compound, an indium salt compound and a sulfur-containing compound, and stirring for 1-2 hours under ultrasonic waves to obtain a mixed solution; the zinc salt compound is ZnCl 2 The indium salt compound is InCl 3 The sulfur-containing compound is thioacetamide;
s3, carrying out condensation-reflux reaction on the mixed solution at the temperature of 80-160 ℃, collecting precipitates, washing and drying to obtain light yellow powder, namely LaNiO 3 @ZnIn 2 S 4 A core-shell type composite photocatalyst.
2. The LaNiO of claim 1 3 @ZnIn 2 S 4 The application of the core-shell composite photocatalyst in catalyzing the photolysis of water to produce hydrogen.
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