CN114100678A - Indium zinc sulfide photocatalyst modified by MXene quantum dot sensitized poly diallyl dimethyl ammonium chloride and preparation and application thereof - Google Patents
Indium zinc sulfide photocatalyst modified by MXene quantum dot sensitized poly diallyl dimethyl ammonium chloride and preparation and application thereof Download PDFInfo
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- CN114100678A CN114100678A CN202111336169.0A CN202111336169A CN114100678A CN 114100678 A CN114100678 A CN 114100678A CN 202111336169 A CN202111336169 A CN 202111336169A CN 114100678 A CN114100678 A CN 114100678A
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- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 title claims abstract description 60
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002096 quantum dot Substances 0.000 title claims abstract description 8
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 title claims abstract description 7
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical class NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000000707 layer-by-layer assembly Methods 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 230000005284 excitation Effects 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 5
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K Indium trichloride Inorganic materials Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010893 electron trap Methods 0.000 description 2
- 238000004924 electrostatic deposition Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000758 substrate Substances 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
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- -1 Transition metal sulfides Chemical class 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001106 transmission high energy electron diffraction data Methods 0.000 description 1
- 239000006163 transport media Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
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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
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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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/325—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups reduction by other means than indicated in C07C209/34 or C07C209/36
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Abstract
The invention discloses an indium zinc sulfide photocatalyst modified by MXene quantum dot sensitized polydiallyldimethylammonium chloride, and preparation and application thereof, wherein the surface of PDDA is modified by ZnIn2S4Nanosheet (ZnIn)2S4/PDDA) has a positive charge surface, and MQDs has a negative charge to trigger electrostatic self-assembly so as to construct ZnIn with a unidirectional cascade charge transport chain2S4a/PDDA/MQDs heterostructure photocatalyst. The invention reduces substituted p-nitroaniline under the excitation of visible light and has high catalysisEfficiency. The composite photocatalytic material has wide practical value and application prospect in the technical field of preparation of heterojunction photocatalytic materials and the field of organic transformation.
Description
Technical Field
The invention relates to a MZnIn modified by QDs/PDDA2S4The preparation of photocatalyst and the application of photocatalytic reduction of paranitroaniline belong to the fields of composite materials, photocatalytic technology and sustainable development of environment and energy.
Background
Transition metal sulfides belong to an important subclass of semiconductor photocatalysts and can promote various valuable redox reactions under mild conditions. One significant advantage of metal sulfides is that their band gap is smaller than that of metal oxides, which in turn ensures that many of them can directly utilize visible light. Ternary metal sulfide ZnIn2S4Has the advantages of smaller band gap, proper energy band structure, unique photoelectric property, excellent photochemical stability, simple preparation process and the like, and is highly concerned by people in the research field of hydrogen production by visible light catalytic decomposition of water and selective oxidation reduction by visible light catalysis. For the current research report, although ZnIn2S4The stability of hydrogen production by visible light catalytic decomposition water and visible light catalytic selective oxidation reduction is high, but the activity of photocatalysis is not high yet, and the level of the photocatalysis cannot reach the level of practical application. To further improve ZnIn2S4Must be modified.
Disclosure of Invention
The invention aims to provide the ZnIn modified by MQDs/PDDA, which has the advantages of high photocatalytic activity, simple process, environmental protection, low cost2S4Preparation method and application of photocatalyst, and prepared MQDs/PDDA modified ZnIn2S4The photocatalyst has the characteristics of photocatalytic reduction of p-nitroaniline and derivatives thereof under the irradiation of visible light and excellent cycle stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
preparation of ZnIn as described above2S4The method of the/PDDA/MQDs heterostructure photocatalyst comprises the following steps:
（1）ZnIn2S4preparing a nano sheet: adding Zn (CH)3COO)2·2H2O and InCl3Adding deionizationThe water was stirred for 30 minutes. Subsequently, an excess of thioacetamide was added to the above solution and stirred for 30 minutes. The mixed solution was then heated to 95 ℃ for 5 hours with vigorous stirring. Cooling to room temperature, centrifugally collecting orange precipitate, and washing with deionized water for several times to obtain ZnIn2S4Nanoplatelets, abbreviated ZIS.
(2) Preparation of MQDs colloidal solution: mixing Ti3AlC2The powder was immersed in hydrofluoric acid and stirred continuously at 60 ℃ for 20 hours. The resulting powder was then washed several times with deionized water and centrifuged at 3500 rpm for 10 minutes to recover the powder particles, and the powder was dried under vacuum at 60 ℃. The obtained powder was then placed in deionized water and sonicated for 30 minutes under a nitrogen blanket. The pH of the mixed solution was adjusted to about 9 with aqueous ammonia, and then the mixed solution was transferred to an autoclave to conduct hydrothermal reaction at 120 ℃ for 6 hours. Finally, the MQDs colloidal solution was filtered through a 220nm filter (25 ppm pH = 9).
(3) ZnIn modified by MQDs sensitized PDDA2S4（ZnIn2S4PDDA/MQDs) composite photocatalyst: ZnIn prepared in the step (1)2S4The nanosheets were added to a mixed solution of PDDA and NaCl (PDDA concentration 10mg/mL, 0.5M NaCl) and vigorously stirred for several minutes. Subsequently, the mixture was centrifuged, and the sample was washed thoroughly with deionized water and dried in air. Thus obtaining the ZnIn with positive charge modified by the surface modification of PDDA2S4Nanosheet (ZnIn)2S4/PDDA, abbreviated as ZP). ZnIn is mixed with a solvent2S4Adding PDDA into a certain volume of MQDs colloidal solution prepared in the step (2), vigorously stirring for several minutes to perform electrostatic self-assembly, centrifuging the mixture, and drying in a vacuum environment to obtain ZnIn2S4a/PDDA/MQDs (noted as ZPM) composite photocatalyst.
The application comprises the following steps: the specific steps of photocatalytic reduction of paranitroaniline are as follows:
(1) taking a certain amount of ultrapure water and ZnIn2S4Photocatalyst with/PDDA/MQDs heterostructure and hole trapping agent Na2SO3The paranitroaniline is evenly stirred in a photocatalytic reaction bottle, nitrogen is introduced, and the paranitroaniline is adsorbed for a certain time in a dark state, so that the paranitroaniline reaches adsorption balance on the surface of the photocatalyst;
(2) under the protection of nitrogen, the system is illuminated, a proper amount of liquid is taken at regular intervals, after the reaction is finished, the system is centrifuged, the catalyst is recovered, and the supernatant of the taken liquid is analyzed by adopting ultraviolet-visible absorption spectrum.
The invention has the following remarkable advantages:
（1）ZnIn2S4the/PDDA/MQDs (ZPM) composite photocatalyst is compared with ZnIn2S4(ZIS) and ZnIn2S4The photocatalytic activity of the/PDDA (ZP) is improved obviously.
（2）ZnIn2S4the/PDDA/MQDs composite photocatalyst has low manufacturing cost, simple production process, macroscopic preparation, environmental protection and easy recovery.
(3) The invention leads the spontaneous electrostatic deposition of MQDs on ZnIn through an electrostatic self-assembly route2S4On the surface of the/PDDA, the photocatalyst has strong circulation stability.
The photocatalytic mechanism:
ZnIn in the invention2S4The ZP binary material is endowed with a surface with positive charges through the uniform packaging of the PDDA polyelectrolyte with positive charges. When negatively charged MQDs are introduced into an aqueous solution of ZP, these oppositely charged building blocks spontaneously bind to each other through strong electrostatic interactions, thereby achieving a large deposition of MQDs on the ZP framework (fig. 2).
A large amount of quaternary ammonium salts in the PDDA have strong electron-withdrawing capability, so that the PDDA also serves as an electron transmission medium while the surface charge characteristic of ZIS is changed, the charge separation efficiency is accelerated, and the performance improvement of the ZP on ZIS is realized (fig. 4). The fermi level position of MQDs-0.39 eV, compared to the conduction band position of ZIS, has enough power to overcome the energy barrier for electron transfer, so MQDs can act as additional electron traps to further enhance the photocatalytic activity of ZPM (fig. 5). Based on halfConductor band theory, under visible light illumination, ZIS generates electron-hole pairs and the corresponding electrons transit to the conduction band, leaving holes in the valence band. Subsequently, the ultra-thin PDDA layer uniformly coated on the surface of ZIS acts as an effective electron relay medium, accelerating electron migration. Due to the close interface contact and alignment with the favorable energy level of the ZIS substrate, the photoelectrons then migrate rapidly to the adjacent MQDs layer, effectively preventing charge recombination and extending the charge lifetime on ZIS. Electrons passing through the ultrathin intermediate PDDA layer and the MQDs layer participate in the reaction of reducing p-nitroaniline, and N is continuously introduced into the reaction system2With addition of Na2SO3As a hole trap to ensure that the photoelectrons are the only active species.
Drawings
FIG. 1 is a transmission electron microscope image of MQDs;
FIG. 2 is ZnIn2S4Zeta potential maps of/PDDA and MQDs;
FIG. 3 is ZnIn2S4Transmission electron micrographs of/PDDA/MQDs;
FIG. 4 is ZP-ion with different PDDA loadingx（x= 5, 10, 15, 20 mg/mL) under visible light irradiation (λ>420 nm) photocatalytic activity of the reduced nitroaniline;
FIG. 5 shows ZPM-x（x= 5, 10, 15, 20 mL) under visible light irradiation (λ>420 nm) photocatalytic activity of the reduced nitroaniline;
FIG. 6 is the cycling stability of ZPM-10 on photocatalytic reduction of nitroaniline;
FIG. 7 is ZnIn2S4，ZnIn2S4XRD pattern of/PDDA/MQDs.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
1.5 mmol of Zn (CH)3COO)2·2H2O and 3 mmol of InCl3250mL ofDeionized water was stirred for 30 minutes. Subsequently, excess thioacetamide (TAA, 8 mmol) was added to the above solution and stirred for 30 minutes. The mixed solution was then heated to 95 ℃ for 5 hours with vigorous stirring. After cooling to room temperature, the orange precipitate was collected by centrifugation and washed several times with deionized water to obtain ZnIn2S4Nanosheets.
② 2.0 g of Ti3AlC2The powder was immersed in 40 mL of 48% hydrofluoric acid and stirring was continued at 60 ℃ for 20 hours. The resulting powder was then washed several times with deionized water and centrifuged at 3500 rpm for 10 minutes to recover the powder particles, and the powder was dried under vacuum at 60 ℃. The powder was then placed in 80mL of deionized water and sonicated for 30 minutes under a nitrogen blanket. The pH of the mixed solution was adjusted to 9 with aqueous ammonia, and then the mixed solution was transferred to an autoclave to conduct hydrothermal reaction at 120 ℃ for 6 hours. Finally, the MQDs colloidal solution was filtered through a 220nm filter (25 ppm pH = 9).
③ mixing ZnIn2S4The nanosheets (100 mg) were added to 10mL of a mixed solution of PDDA and NaCl (PDDA concentration 10mg/mL, 0.5M NaCl) and vigorously stirred for 30 minutes. Thereafter, the mixture was centrifuged, and sufficiently washed with deionized water to thereby obtain ZnIn surface-modified by PDDA2S4Nanosheets (ZP-10) and dried in air. Adding prepared ZP-10 (100 mg) into 10mL of colloidal solution of MQDs (25 ppm, pH = 9), stirring vigorously for 30 min, centrifuging the mixture, and drying at 60 deg.C under vacuum to obtain ZnIn2S4a/PDDA/MQDs (noted as ZPM-10) heterostructure photocatalyst.
And fourthly, uniformly mixing 10mg of ZPM-10 composite photocatalyst, 40 mg of sodium sulfite as a hole trapping agent and 5ppm of 30 mL of paranitroaniline, continuously introducing nitrogen (80 mL/min), violently stirring for 30 minutes in a dark environment to reach adsorption and desorption equilibrium, and then placing under a 300W xenon lamp (420 nm) for illumination for 25 minutes. A sample of 3ml of the solution was taken at the given time (0, 5, 10, 15, 20, 25 min), centrifuged to give a supernatant, and the supernatant was analyzed with a UV-visible spectrophotometer.
The conversion rate of the p-nitroaniline by photocatalytic reduction is about 93.64%.
Example 2
1.5 mmol of Zn (CH)3COO)2·2H2O and 3 mmol of InCl3250mL of deionized water was added and stirred for 30 minutes. Subsequently, excess thioacetamide (TAA, 8 mmol) was added to the above solution and stirred for 30 minutes. The mixed solution was then heated to 95 ℃ for 5 h with vigorous stirring. After cooling to room temperature, the orange precipitate was collected by centrifugation and washed several times with deionized water to obtain ZnIn2S4Nanosheets.
② 2.0 g of Ti3AlC2The powder was immersed in 40 mL of 48% hydrofluoric acid and stirring was continued at 60 ℃ for 20 hours. The resulting powder was then washed several times with deionized water and centrifuged at 3500 rpm for 10 minutes to recover the powder particles, and the powder was dried under vacuum at 60 ℃. The powder was then placed in 80mL of deionized water and sonicated for 30 minutes under a nitrogen blanket. The pH of the mixed solution was adjusted to 9 with aqueous ammonia, and then the mixed solution was transferred to an autoclave to conduct hydrothermal reaction at 120 ℃ for 6 hours. Finally, the MQDs colloidal solution was filtered through a 220nm filter (25 ppm pH = 9).
③ mixing ZnIn2S4The nanosheets (100 mg) were added to 10mL of a mixed solution of PDDA and NaCl (PDDA concentration 10mg/mL, 0.5M NaCl) and vigorously stirred for 30 minutes. Thereafter, the mixture was centrifuged, and sufficiently washed with deionized water to thereby obtain ZnIn surface-modified by PDDA2S4Nanosheets (ZP-10) and dried in air. Adding prepared ZP-10 (100 mg) into 15mL of colloidal solution of MQDs (25 ppm, pH = 9), stirring vigorously for 30 min, centrifuging the mixture, and drying at 60 deg.C under vacuum to obtain ZnIn2S4a/PDDA/MQDs (noted as ZPM-15) heterostructure photocatalyst.
Mixing 10mg of ZPM-15 photocatalyst, 40 mg of hole trapping agent sodium sulfite and 5ppm of 30 mL of paranitroaniline uniformly, continuously introducing nitrogen (80 mL/min), stirring vigorously for 30 minutes in a dark environment to reach adsorption and desorption equilibrium, and then placing under a 300W xenon lamp (420 nm) for illumination for 25 minutes. A sample of 3ml of the solution was taken at the given time (0, 5, 10, 15, 20, 25 min), centrifuged to give a supernatant, and the supernatant was analyzed with a UV-visible spectrophotometer.
The conversion rate of the p-nitroaniline by photocatalytic reduction is about 75%.
FIG. 1 is a TEM image of MQDs with an average size of about 2.4nm showing MXene materials (Ti) in the form of quantum dots3C2) The successful preparation.
FIG. 2 is a Zeta potential diagram of ZP and MQDs. ZIS packaged by PDDA is positively charged, MQDs are negatively charged, and strong evidence is provided for the ZPM composite photocatalyst formed by electrostatic self-assembly.
Fig. 3 is a TEM image of ZPM. TEM images confirmed that the ZIS surface was uniformly wrapped by the ultra-thin PDDA layer. Furthermore, the MQDs are randomly distributed on the two-dimensional framework of ZIS encapsulated by PDDA, which can be distinguished by the black circles in the figure, wherein the 0.26 nm lattice stripe is Ti3C2The (0110) plane of (MQDs), the SAED pattern of ZPM verifies the characteristics of the (114) and (006) planes of ZIS and the (0110) plane of MQDs.
FIG. 4 is a graph comparing ZP-values for different PDDA loadings on ZIS nm chipsxThe photocatalytic performance of the photocatalytic reduction of paranitroaniline. The preparation process of the ZP-5 composite material is similar to the step (c) of the example 1: ZnIn is mixed with a solvent2S4The nanosheets (100 mg) were added to 10mL of a mixed solution of PDDA and NaCl (PDDA concentration 5 mg/mL, 0.5M NaCl) and vigorously stirred for 30 minutes. Thereafter, the mixture was centrifuged, and sufficiently washed with deionized water to thereby obtain ZnIn surface-modified by PDDA2S4Nanosheets (ZP-5) and dried in air. Similarly, the preparation of the ZP-15 and ZP-20 composite photocatalysts is similar to the above steps, and only the concentration of PDDA is changed to 15 mg/mL and 20 mg/mL respectively. As can be seen from FIG. 4 and Table 1, unmodified ZIS only has a 23.05% conversion rate under 25 minutes of light, and the conversion rates of tightly packed ZP-5, ZP-10, ZP-15 and ZP-20 by PDDA were improved to different degrees under the same experimental conditions, respectively 30.25%,41.39%,39.71% and 36.28%. And the highest conversion rate of ZP-10 is achieved, which is strongThe effect of the non-conjugated polymer PDDA as an electron transport medium for enhancing electron transfer is strongly demonstrated.
TABLE 1 ZP with different PDDA loadingsx（x= 5, 10, 15, 20 mg/mL) under visible light irradiation (λ>420 nm) photocatalytic activity for the reduction of nitroanilines
FIG. 5 is a graph of ZPM-xThe photocatalytic performance of the photocatalytic reduction of paranitroaniline. The preparation process of the ZPM-5 composite material is similar to the step three of the example 1: adding ZP-10 (100 mg) into 5mL of colloidal solution of MQDs (25 ppm, pH = 9), stirring vigorously for 30 min, centrifuging the mixture, and drying at 60 deg.C under vacuum to obtain ZnIn2S4a/PDDA/MQDs (noted as ZPM-5) heterostructure photocatalyst. Similarly, the preparation of the ZPM-20 composite photocatalyst is similar to the above steps, and only the addition amount of MQDs is increased to 20 mL. As can be seen from FIG. 5 and Table 2, the conversion rates after electrostatic deposition of ZP-10 at the same experimental conditions were improved to different degrees, 47.96%, 93.64%, 79.32% and 50.92% for ZP-5, ZPM-10, ZPM-15 and ZPM-20, respectively, compared to ZP-10. And ZPM-10 reached the highest conversion, which strongly confirms the role of the non-conjugated polymer PDDA as an interlayer relay and MQDs as additional electron traps to enhance electron transport.
TABLE 2 ZPM-x（x= 5, 10, 15, 20 mL) under visible light irradiation (λ>420 nm) photocatalytic activity for the reduction of nitroanilines
FIG. 6 is a test of the cycling stability of ZPM-10. It can be seen that after 5 cycles of ZPM-10, the photocatalytic activity does not decline dramatically, suggesting that ZPM has potential application value as a robust and effective catalyst.
Fig. 7 is an XRD pattern of ZIS and ZPM. As shown, ZIS is similar to the XRD pattern of ZPM at 21.6o, 27.7o, 30.4o, 39.8o, 47.2oAnd 52.4 ℃ are derived from the crystal planes of ZnIn2S4 (006), (102), (104), (108), (110) and (116) of the hexagonal system (JCPDS No. 65-2023). ZIS XRD patterns similar to ZPM indicate that the crystal structure of ZIS is preserved after PDDA encapsulation and electrostatic MQDs deposition. Furthermore, no peaks from MQDs are evident in the XRD spectrum of ZPM, possibly due to weak MQDs peak intensities, or these peaks are obscured by the main diffraction peak of the ZIS substrate.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
- A preparation method of an indium zinc sulfide photocatalyst modified by MXene quantum dot sensitized polydiallyldimethylammonium chloride is characterized by comprising the following steps: which comprises the following steps:(1) preparation of MQDs colloidal solution:mixing Ti3AlC2Immersing the powder in hydrofluoric acid, continuously stirring for 20 hours at 60 ℃, then washing with deionized water to obtain powder, centrifuging at 3500 rpm for 10 minutes to recover powder particles, and drying the powder in a vacuum environment; then putting the obtained powder into deionized water, performing ultrasonic treatment for 60-120 minutes under the environment of nitrogen protection, adjusting the pH value of the mixed solution to 9 by using ammonia water, then transferring the mixed solution into a high-pressure kettle for hydrothermal reaction, and finally filtering the obtained mixed solution through a filter membrane of 220nm to obtain a MQDs colloidal solution;（2）ZnIn2S4preparation of a/PDDA/MQDs composite photocatalyst:ZnIn is mixed with a solvent2S4Adding the nanosheet into a mixed solution of PDDA and NaCl, vigorously stirring for 30-60 minutes, centrifuging the mixture at 10000 rpm for 5 minutes, fully washing a sample with deionized water, and drying in air to obtain the PDDA surface modification modified positive bandCharged ZnIn2S4Nanosheet ZnIn2S4(ii) PDDA; then ZnIn is put into2S4adding/PDDA into the MQDs colloidal solution prepared in the step (1), vigorously stirring for 30-60 minutes to perform electrostatic self-assembly, then centrifuging the mixture at 10000 rpm for 5 minutes, and finally drying in a vacuum environment to obtain ZnIn2S4a/PDDA/MQDs heterostructure photocatalyst.
- 2. The method of claim 1, wherein: the temperature of the hydrothermal reaction in the step (1) is 120 ℃, and the reaction time is 6 hours.
- 3. The method of claim 1, wherein: the concentration of the MQDs colloidal solution prepared in the step (1) is 25ppm, and the pH = 9.
- 4. The method of claim 1, wherein: in the step (2), PDDA and MQDs are orderly deposited on ZnIn by electrostatic acting force2S4And (4) nano-chips.
- 5. The method of claim 1, wherein: in the step (2), in the mixed solution of PDDA and NaCl, the concentration of PDDA is 10mg/mL, and the concentration of NaCl is 0.5M.
- 6. The MXene quantum dot sensitized polydiallyldimethylammonium chloride modified indium zinc sulfide photocatalyst prepared by the preparation method of any one of claims 1-5.
- 7. The application of the MXene quantum dot sensitized polydiallyldimethylammonium chloride modified indium zinc sulfide photocatalyst as claimed in claim 6, wherein the photocatalyst comprises: the indium zinc sulfide photocatalyst modified by MXene quantum dot sensitized polydiallyldimethylammonium chloride is used for photocatalytic reduction of paranitroaniline in a water phase under visible light.
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