CN113171784A - Preparation method of MXene modified cadmium selenide quantum dot heterogeneous composite material for photolysis of water to produce hydrogen - Google Patents
Preparation method of MXene modified cadmium selenide quantum dot heterogeneous composite material for photolysis of water to produce hydrogen Download PDFInfo
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- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical class [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002096 quantum dot Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000006303 photolysis reaction Methods 0.000 title claims abstract description 10
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
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- 238000005119 centrifugation Methods 0.000 claims description 3
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- 239000003381 stabilizer Substances 0.000 claims description 3
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 claims description 2
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- 230000001699 photocatalysis Effects 0.000 description 23
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000000707 layer-by-layer assembly Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal chalcogenide Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a preparation method of an MXene modified cadmium selenide quantum dot heterogeneous composite material for hydrogen production by water photolysis. CdSe quantum dots, surface ligands AET and Ti3C2Tx(MXene) is used as a raw material, and the MXene modified CdSe QDs photocatalyst is obtained through electrostatic interaction force, and the MXene loading capacity with the optimal performance is explored. The invention uses MXene modified CdSe QDs as the cocatalyst for photolysis water to produce hydrogen for the first time, has higher catalytic activity, simple preparation process, reliable design principle, low generation cost and short period, and is beneficial to the sustainable development of environment and energy.
Description
Technical Field
The invention relates to a photocatalyst for producing hydrogen by photolyzing water by using MXene modified cadmium selenide quantum dots, belonging to the technical field of photocatalytic material preparation and solar energy conversion.
Background
For economic and social development, mankind has burned a large amount of fossil energy such as coal and petroleum for the past hundred years and released various harmful gases into the atmosphere. According to the fossil fuel consumption rate curve proposed by Hubbert, the peak demand for oil and coal may come in the next decade. Therefore, the development of renewable, eco-friendly energy sources has been a final goal around the minds of material scientists for many years. Hydrogen, as a clean, renewable fuel, is one of the most potential alternatives to traditional fossil energy sources. In this context, solar-driven semiconductor photocatalyst water splitting systems are considered as a promising measure to address energy shortages and environmental issues. TiO since 19722Scientists explored a variety of photocatalytic hydrogen production systems since they first reported splitting water into hydrogen and oxygen under ultraviolet light. Since then, the introduction of a study on hydrogen production using semiconductor photocatalysts was opened. The semiconductor can be used for photocatalytic hydrogen production, and on one hand, the band gap of the semiconductor is required to be narrow, so that more sunlight can be utilized as much as possible; on the other hand, the conduction band potential of the semiconductor is required to be lower than the precipitation potential of hydrogen production, and electrons on the conduction band can be used for photocatalytic decomposition of water to produce hydrogen, that is, not all semiconductors are available. Therefore, the exploration of an efficient and clean semiconductor photocatalytic water decomposition system is a major problem which needs to be solved urgently by modern human beings.
Disclosure of Invention
The invention aims to provide a preparation method and application of a CdSe @ AET-MXene photocatalyst which is low in preparation cost, simple in production process and environment-friendly, and CdSe @ AET-MXene photocatalyst is prepared from CdSe quantum dots, surface ligands AET and Ti3C2Tx(MXene) is used as a raw material, and the MXene modified CdSe QDs photocatalyst is obtained through electrostatic interaction force, and the MXene loading capacity with the optimal performance is explored. The zero-dimensional-two-dimensional (0D-2D) binary heterojunction can perform photocatalytic water decomposition and nitro under visible lightThe reduction characteristic and the high catalytic activity.
In order to achieve the purpose, the invention adopts the following technical scheme:
an MXene modified CdSe quantum dot heterogeneous composite material for photolyzing water to generate hydrogen is prepared from CdSe quantum dots (CdSe QDs), 2-mercaptoethylamine hydrochloride (AET) and Ti3C2Tx(MXene).
The preparation method of the MXene modified cadmium selenide quantum dot heterogeneous composite material for photolysis of water to produce hydrogen comprises the following specific steps:
(1) preparation of CdSe quantum dots: by Cd in the presence of AET as a stabilizer2+The reaction with NaHSe solution prepares water-soluble AET-coated CdSe QDs, specifically, 200mL of 2 mmol/L CdCl are added into a 250 mL three-neck flask2·2.5H2O in water, continuously introducing N2Stirring at the speed of 1000-; another 0.632g of NaBH4Dissolving in 10mL of deionized water, adding 0.2106g of selenium powder, stirring in ice bath at low speed for 2 hours and continuously introducing N2To prevent oxidation and prepare an oxygen-free NaHSe aqueous solution; then 5mL of freshly prepared NaHSe aqueous solution was drawn off with a pipette and injected rapidly into the above CdCl2•2.5H2In the O aqueous solution, the solution turns orange yellow, is stirred vigorously at 80-85 ℃ for reflux reaction for 4 hours, is cooled to room temperature after the reaction is finished, is added with ethanol with the same volume and is stirred vigorously for 0.5-1 hour, is kept stand for several hours, is removed of supernatant, is taken out, is washed with ethanol for 3-5 times (40 mL each time), is centrifuged, is dried (vacuum drying, the temperature is 50-70 ℃) to obtain the CdSe quantum dots with positive electricity;
(2) preparation of MXene: 1g of lithium fluoride and 10mL of hydrochloric acid (9 mol L) were added in an oil bath at 35 deg.C-1) Is used to etch 1g of Ti3AlC2Powder, forming multiple layers of Ti after 24 hours3C2Tx. Washing the product with deionized water until the supernatant has a pH above5. Then the multi-layer Ti3C2TxThe powder was added to 200mL of deionized water and placed in Ar or N2The layers were separated by sonication in a water bath for 1h under flow-through conditions. After centrifugation at 3500 rpm for 1 hour, a dark green supernatant was collected. The delaminated Ti was determined by filtering a known volume of supernatant through a Celgard membrane and measuring the weight of the membrane after drying3C2TxThe concentration of (c).
(3) Preparation of CdSe QDs-MXene composite material: dispersing the AET-coated CdSe QDs in the step (1) in deionized water, and performing ultrasonic treatment to obtain a colloid solution (4 mg/mL) of the positively charged CdSe QDs. Subsequently, the negatively charged colloid Ti3C2Tx(2 mg/mL) solution was added to the AET capped CdSe QDs solution and stirred under blocking conditions for 2-5 hours. The mixture was then centrifuged, washed with deionized water and dried in an oven at 60 ℃ to obtain the CdSe QDs-MXene heterostructure.
The invention is formed by combining the components in an electrostatic self-assembly mode, CdSe QDs are positively charged, and MXene is negatively charged.
The application comprises the following steps: the MXene modified cadmium selenide quantum dot heterogeneous composite material is applied to visible light photolysis water hydrogen production as a photocatalyst.
The invention has the following remarkable advantages:
(1) the invention utilizes the electrostatic self-assembly technology to trigger a large amount of positively charged CdSe QDs to be attracted to the MXene surface, so as to form a binary heterostructure. Due to the good energy level arrangement, the unique and compact electrostatic combination mode and the excellent structural advantages of the CdSe @ AET-MXene binary heterostructure, the charge separation and transfer are accelerated, the photocatalytic hydrogen production performance is obviously enhanced, and meanwhile, the CdSe @ AET-MXene binary heterostructure has good light stability and obvious apparent quantum yield under the irradiation of visible light.
(2) MXene has good electronic conductivity, structural stability and larger specific surface area, can be used as a cocatalyst to improve the photocatalytic performance, and is beneficial to the hydrogen production reaction. Meanwhile, the CdSe QDs photocatalyst modified by MXene serving as a cocatalyst forms an effective cascade charge transfer channel, and has the characteristics of high photoactivity, low manufacturing cost, simple production process, macroscopic preparation, environmental friendliness, easiness in recovery and the like.
(3) Currently, there is still a lack of an easy, green, and efficient structure for constructing a cascade charge transport channel in all transition metal chalcogenide-based heterostructures. In addition, no interface engineering and fine nanostructure design between transition metal chalcogenide and MXene promoter has been reported to improve interface charge transport efficiency. However, when these two materials are combined, the space charge transfer can be reasonably adjusted to collect and convert solar energy.
(4) The step of synthesizing colloidal CdSe quantum dots can be simply understood as Se2-Introduction of precursor containing Cd2+The precursor reacts with an aqueous solution of AET, wherein the AET mainly acts as a surface ligand and a stabilizer to coat a layer of organic molecules with positive charges on the outer surface of the CdSe quantum dot, namely positively charged protonic amino (-NH)3 +) And (4) surrounding. Due to mutual repulsion of the same charges, each CdSe quantum dot is promoted to be uniformly dispersed in an aqueous solution, so that the CdSe quantum dot is quite stable and positively charged.
Drawings
FIG. 1 is a multilayer Ti3C2And a single layer of Ti3C2；
FIG. 2 is a transmission electron microscope image of 2% by mass of CdSe QDs-2% MXene photocatalyst prepared in example;
FIG. 3 is a graph of hydrogen production rates of MXene-modified CdSe QDs loaded with different mass ratios prepared in the examples;
FIG. 4 is a graph of hydrogen production rate of CdSe QDs 2% MXene prepared in the example with a mass ratio of 2% under different conditions of the hole trapping agent;
FIG. 5 is a hydrogen production cycle chart of (a) pure CdSe QDs and (b) binary heterojunction CdSe QDs-2% MXene prepared in the examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The following specifically describes the preparation of the MXene modified cadmium selenide quantum dot heterogeneous composite material for photolysis of water to produce hydrogen in the embodiment of the invention.
(1) Preparation of CdSe @ AET quantum dots
1) Preparing oxygen-free NaHSe solution
(a) 10mL of water is measured by a measuring cylinder/pipette and placed in a 25 mL three-necked bottle, and the other two bottle mouths are sealed except for a middle sample inlet.
(b) Fixed device back-through N2Bubbling was performed below the surface of the liquid, and the rotation speed was set at 300 rpm, and the liquid was cooled in an ice bath.
(c) Weighing 0.6320NaBH4And quickly added to dissolve.
(d) 0.2106 selenium powder is weighed, added into a three-neck flask and then quickly sealed, and timing is started for 2 hours to prepare an oxygen-free NaHSe solution.
2) Preparation of CdCl2Solutions of
(a) Preparation of 0.01M CdCl2 (aq) 500 mL：CdCl2•2.5H21.1416 g of O crystal was put into a 500 mL volumetric flask and dissolved in water to a constant volume.
(b) 200mL of the prepared solution is measured by a 250 mL measuring cylinder, poured into a 250 mL three-necked bottle, provided with a reflux device, introduced with nitrogen for 1h, bubbled under the liquid level, and a vent is sealed.
(c) The rotation speed is set at 1200 rpm, the oil bath temperature is set at 80 ℃, and if the temperature is unstable, the temperature can be set to 81-82 ℃, and the window is closed/the fume hood fan is closed.
(d) 250mg of AET (mercaptoethylammonium) was added followed by 280 uL of HCl (0.01M).
3) Preparation of QDs
(a) After the NaHSe preparation was complete, the stirring was stopped.
(b) Taking 5mL pipette, pulling out the plug under the condition of ventilation, sucking 5mL solution stably, and injecting CdCl rapidly2In solution, at which time a change in solution was observedIs a uniform orange-yellow color.
(c) The reaction was started for 4h and after the reaction was complete, the solution was removed from the oil bath and cooled for one hour.
(d) Pouring the cooled colloidal solution into absolute ethyl alcohol, stirring for 30 min, precipitating for 12 h, centrifugally drying, and finally grinding into a powder sample.
(2) Preparation of MXene nano-sheet
1) First, multi-layered Ti is synthesized3C2TxBy adding 1g of lithium fluoride and 10mL of hydrochloric acid (9 mol/L) with 1g of Ti3AlC2The powder mixture was left at 35 ℃ for 24 h.
2) The product was then washed with deionized water until the pH of the supernatant was above 5. Then a plurality of layers of Ti3C2TxThe powder was added to 200mL of deionized water and mixed in N2The layers were separated by sonication for 1 h.
3) After centrifugation at 3500 rpm for 1 hour, the dark green supernatant was collected. The delaminated Ti was determined by filtering a known volume of supernatant through a Celgard membrane and measuring the weight of the membrane after drying3C2TxThen the layered Ti3C2TxThe colloid was diluted to a concentration of 2 mg/mL.
(3) Preparation of CdSe @ AET-MXene heterojunction photocatalyst
1) Weighing a certain amount of CdSe @ AET powder, and adding into 10mL of ultrapure water to form an orange yellow solution;
2) adding a certain amount of MXene colloidal solution, and stirring for 2 hours to fully assemble the MXene colloidal solution together;
3) transferring the mixed solution into a centrifuge tube with the capacity of 50 mL, centrifuging, cleaning and drying at 60 ℃.
4) The resulting powder was collected.
The specific amounts of CdSe @ AET powder and MXene colloidal solution are given in the following table:
said different usesThe MXene modified CdSe QDs photocatalyst is irradiated under visible light, has the best photocatalytic activity when the mass ratio is 2 percent, and the photocatalytic hydrogen production rate can reach 204 mu mol.h-1·g-1。
The application comprises the following steps: the photocatalytic water decomposition hydrogen production performance test method specifically comprises the following steps:
(a) a quartz reactor is utilized to carry out photocatalytic reaction on a photocatalytic hydrogen production system. 10 mg of catalyst is dispersed in 5mL of aqueous solution with 0.5mL of lactic acid as a hole trapping agent to carry out photocatalytic hydrogen production reaction. The photocatalytic system is completely degassed and is equipped with a 420nm cut-off filter (. lamda.)>420 nm) 300W xenon lamp. According to H2H before the reaction2The amount released was evaluated for photocatalytic activity. A continuous magnetic stirrer was applied to the bottom of the reactor to keep the catalyst in suspension throughout the experiment. The hydrogen produced was monitored periodically by an on-line gas chromatograph (Shimadzu GC-8A, MS-5A column, argon as carrier gas).
(b) Collecting and analyzing the data in step (a) for comparison.
As can be seen from (a) in FIG. 1, Ti3AlC2After the powder reacts with hydrochloric acid (HCl) and lithium fluoride (LiF) to etch the aluminum layer, the product forms accordion-shaped Ti3C2And (5) structure. As can be seen from (b) in FIG. 1, under a protective atmosphere (N)2) Next, a plurality of layers of Ti are formed by megasonic waves3C2The structure is crushed into Ti3C2Micro-tablets, i.e. MXene (Ti)3C2Tx) The nano-sheet has an average thickness of about 1.40 nm, and meets the characteristics of a two-dimensional nano-sheet material.
As can be seen from (a) in FIG. 2, after the CdSe QDs are modified by MXene, a large number of 0D CdSe quantum dots are deposited on the surface of the 2D MXene nanosheet, and the CdSe QDs/MXene hybrid product presents a 0D-2D structure. From a further magnified view of (b) in fig. 2, it can be seen that the spatially dispersed CdSe quantum dots are uniformly deposited on the Mxene surface. From fig. 2 (c), a clear lattice fringe of CdSe quantum dots and MXene can be seen, indicating that its crystallinity is high. Lattice spacing of 0.35 nm and 0.26 nm, respectively, (111) in the cubic phase with CdSeA face and Ti3C2TxThe (010) planes of MXene have uniform interplanar spacings.
As can be seen from FIG. 3, all samples were examined for the photocatalytic hydrogen generation performance under irradiation of visible light (. lamda. gtoreq.420 nm) under the lactic acid aqueous solution condition. Exciting is that Ti3C2TxThe coupling of NSs to CdSe quantum dots does result in a significant enhancement of photocatalytic activity. Pure CdSe quantum dots with lower photocatalytic H2The release rate was 91. mu. mol. h-1·g-1. With Ti3C2TxThe photocatalytic activity of the CdSe-MXene is gradually improved until the Ti content is increased3C2TxThe dosage is 2 percent (204 mu mol. h)-1·g-1) This strongly demonstrates that MXene in combination with CdSe quantum dots facilitates electron transfer in 0D-2D structures due to intimate interfacial contact with the MXene substrate and its proper energy level arrangement. In contrast, Ti3C2TxAt NSs loading of 4%, the photocatalytic activity is weaker due to the "screening effect" caused by excessive addition of MXene.
As can be seen in FIG. 4, the photoactivity of CdSe QDs-2% M is significantly affected by the type of sacrificial reagent. 5 hole trapping sacrificial agents such as methanol, ethanol, ethylene glycol, glycerol, lactic acid and the like are selected to detect the photocatalytic hydrogen production of CdSe QDs-2% M, wherein the lactic acid has the best efficiency due to higher deprotonation efficiency. The deprotonation of the functional groups in the lactic acid can effectively change the surface behavior of the photocatalyst, thereby controlling the whole adsorption process.
As can be seen from fig. 5, it is worth noting that the photo-stability of the photocatalyst is a crucial factor in the photocatalytic reaction. Examination of the cyclic photocatalytic hydrogen evolution performance by carrying out 6 photocatalytic reactions in succession (each cycle lasting 2 h) as expected, CdSe QDs-2% MXene showed a rather stable photocatalytic hydrogen evolution activity (b in fig. 5) even after 6 cycles in succession, whereas under the same conditions the photostability of pure CdSe QDs was poor (a in fig. 5), indicating that the formation of hybridization favoured the improvement of poor photostability.
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)
1. The MXene modified cadmium selenide quantum dot heterogeneous composite material for photolysis of water to produce hydrogen is characterized in that: the composite material is prepared from cadmium selenide quantum dots CdSe QDs, 2-mercaptoethylamine hydrochloride AET and Ti3C2TxAnd (4) forming.
2. The preparation method of the MXene modified cadmium selenide quantum dot heterogeneous composite material for photolysis of water to produce hydrogen according to claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
(1) preparation of CdSe QDs:
by Cd in the presence of AET as a stabilizer2+The reaction between the CdSe QDs coated by water-soluble AET and NaHSe solution is adopted to prepare CdSe QDs coated by water-soluble AET;
(2) preparation of MXene:
first, a mixture of 1g of lithium fluoride and 10mL of hydrochloric acid was added to etch 1g of Ti in a 35 deg.C oil bath3AlC2Powder, forming multiple layers of Ti after 24 hours3C2TxWashing the product with deionized water until the supernatant has a pH above 5, and then subjecting the multilayer Ti to a treatment3C2TxThe powder was added to 200mL of deionized water and placed in Ar or N2The layers were separated by sonication in a water bath for 1h under flow-through conditions, after centrifugation at 3500 rpm for 1 hour, a dark green supernatant was collected, a known volume of the supernatant was filtered through Celgard membranes and the weight of the dried membranes was measured to determine the delaminated Ti3C2TxThe concentration of (c);
(3) preparation of CdSe QDs-MXene composite material
Firstly dispersing the AET-coated CdSe QDs in the step (1) in deionized water, obtaining a positively charged CdSe QDs colloidal solution through ultrasonic treatment, and then adding Ti with negative charge3C2TxColloidal solution, and stirring under closed condition for 2-5After the hour, the mixture was centrifuged, washed with deionized water, and dried in an oven at 60 ℃ to obtain the MXene-modified cadmium selenide quantum dot heterogeneous composite material CdSe QDs-MXene.
3. The method of claim 2, wherein: the preparation of CdSe QDs specifically comprises the following steps: CdCl was placed in a three-necked flask2•2.5H2Dissolving O in deionized water and adding N2Removing air for 1h, then adding AET, adjusting the pH value of the solution to 4-5 by using 1M HCl aqueous solution, then rapidly adding a freshly prepared oxygen-free NaHSe solution under vigorous stirring, refluxing for 4h at 80-85 ℃, cooling to room temperature after the reaction is finished, adding equal volume of ethanol, vigorously stirring for 0.5-1h, standing for several hours, removing the supernatant, washing the precipitate with ethanol for 3-5 times, centrifuging, and drying to obtain the positive-charged AET-coated CdSe QDs.
4. The production method according to claim 3, characterized in that: cd [ Cd ]2+：Se2-: the initial molar ratio of AET was 3: 2: 5.
5. the method of claim 2, wherein: the concentration of the hydrochloric acid in the step (2) is 9 mol/L.
6. The method of claim 2, wherein: the CdSe QDs colloidal solution in the step (3) has the concentration of 4 mg/mL and Ti3C2TxThe concentration of the colloidal solution was 2 mg/mL.
7. The use of the MXene-modified cadmium selenide quantum dot heterogeneous composite material of claim 1, wherein: the MXene modified cadmium selenide quantum dot heterogeneous composite material is applied to visible light photolysis water hydrogen production as a photocatalyst.
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