CN113083328B - MoS 2 Preparation method and application of Ag-In-Zn-S quantum dot co-modified by hole extraction functionalized carbon quantum dot - Google Patents
MoS 2 Preparation method and application of Ag-In-Zn-S quantum dot co-modified by hole extraction functionalized carbon quantum dot Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002096 quantum dot Substances 0.000 title claims abstract description 43
- 238000000605 extraction Methods 0.000 title claims abstract description 35
- 229910007609 Zn—S Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000005406 washing Methods 0.000 claims abstract description 42
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 23
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 23
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 21
- 239000004201 L-cysteine Substances 0.000 claims abstract description 19
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004246 zinc acetate Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 30
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 17
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
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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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/23—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of nano material preparation, relates to a photocatalyst, and in particular relates to a MoS 2 The preparation method of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dots (fCDs) comprises the following steps: dissolving silver nitrate, indium nitrate, zinc acetate and L-cysteine in water, and regulating the pH value to 8.5 by using a NaOH solution; continuously adding fCDs precursor and thioacetamide, stirring uniformly by ultrasonic, performing hydrothermal reaction for 2-4 hours at 110-140 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs; mixing the prepared AIZS/fCDs with MoS 2 The precursor is dissolved in water, mechanically stirred for 8 to 16 hours, and centrifugally washed to obtain the catalyst. The invention also relates to the prepared MoS 2 The AIZS/fCDs photocatalyst is applied to photocatalytic hydrogen production. The invention has simple process, low cost and easy obtainment, is convenient for mass production, is nontoxic and harmless, and meets the environmental protection requirement. Under the excitation of visible light, the photo-generated holes and electrons are respectively and rapidly transferred to MoS 2 And on fCDs, the recombination is reduced, so that more electrons can be used for hydrogen production reaction, and the photocatalytic performance is improved.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, relates to a photocatalyst, and in particular relates to a MoS 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs).
Background
Photocatalytic water splitting is considered one of the most desirable methods for producing hydrogen directly from continuous solar energy and water. Visible light occupies about 43% of sunlight and plays a key role in better solar energy utilization, however, the utilization rate is far lower than expected. Quantum Dots (QDs) are considered to be the most promising visible light active photocatalyst candidate particles due to unique Quantum confinement effects, desirable optical properties, and large specific surface area. Compared with the traditional II-VI quantum dots, the cadmium-free I-III-VI quantum dots have wide attention in the field of photocatalysis due to the adjustable forbidden bandwidth and low toxicity of components, and are the most promising visible light activity candidate quantum dots. However, the charge separation efficiency is low, and the improvement of the catalytic activity is severely limited, so that the further improvement of the charge separation efficiency of the photocatalyst is particularly important.
In photocatalytic research, cocatalysts play an important role in improving charge separation efficiency, such as molybdenum disulfide (MoS) with high conductivity 2 ) Nanoplatelets, excellent electrical conductivity makes them excellent electron promoters; carbon quantum dots (CDs) can be used as electron donors and acceptors (electron mediums) due to the existence of multiple energy levels, and the energy band arrangement plays a key role in the design of a photocatalyst, and the CDs are expected to realize efficient hole transfer by adjusting the Highest Occupied Molecular Orbital (HOMO) energy level to serve as a hole transport material.
In view of the above analysis, the present invention modifies ferrocenecarboxylic acid (FcA)Forming hole extraction functionalized carbon dots (fCDs) with hole extraction function In CDs, compounding the carbon dots with Ag-In-Zn-S quantum dots by an In-situ synthesis mode to form AIZS/fCDs, and loading the AIZS/fCDs on MoS by a mechanical stirring method 2 On the nano-sheet and used for research in the field of photocatalytic hydrogen production.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a MoS 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs).
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising the steps of:
A. dissolving silver nitrate, indium nitrate, zinc acetate and L-cysteine in water, and adjusting the pH value to 8.5 by using a 1M NaOH solution, wherein the silver nitrate is prepared by the following steps: indium nitrate: zinc acetate: l-cysteine: the molar volume ratio of water is 0.17-0.51 mmol:0.17 to 1.7mmol:0.17 to 0.85mmol:5mmol:5.5mL, preferably 0.34mmol:1.7mmol:0.85mmol:5mmol:5.5mL;
B. continuously adding fCDs precursor and thioacetamide into the solution, stirring uniformly by ultrasonic, performing hydrothermal reaction for 2-4 h at 110-140 ℃ and preferably performing hydrothermal reaction for 4h at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs, wherein the fCDs precursor is prepared by the steps of: thioacetamide: the molar volume ratio of water is 3.48-17.4 mmol:0.4 to 3.2mmol:5.5mL, preferably 14mmol:3.2mmol:5.5mL of water in step A;
C. mixing the prepared AIZS/fCDs with MoS 2 Dissolving the precursor in water, mechanically stirring for 8-16 h, preferably 12h, centrifuging and washing to obtain MoS 2 AIZS/fCDs, wherein the AIZS/fCDs: moS (MoS) 2 Precursor: the mass volume ratio of water is 100mg: 3-15 mg:10mL, preferably 100mg:9mg:10mL.
In a preferred embodiment of the present invention, the fdds precursor in step B is prepared by the following method: dissolving carbon quantum dots (CDs) and FcA in dimethyl sulfoxide, carrying out solvothermal reaction for 2-4 hours at 110-140 ℃ and preferably at 140 ℃ until the volume reaches 20mL, centrifuging and washing to obtain the carbon quantum dots (CDs): fcA mass volume ratio is 3-15 mg:0.48 to 2.4mg, preferably 12mg:1.92mg.
In a preferred embodiment of the present invention, in the step C, the MoS 2 A precursor, its preparation method: 1mmol (NH) 4 ) 6 Mo 7 O 24 4H 2 O and 30mmol of CH 4 N 2 S is dissolved in 35mL deionized water, stirred vigorously for 20min to form a uniform solution, put into a stainless steel high-pressure vessel lined with Teflon of 50mL, reacted hydrothermally at 160-240 ℃ for 12-24 h, preferably at 220 ℃ for 18h, and washed with 0.1M HCl to completely remove NH 4 + Drying at 60deg.C under vacuum to obtain the final product.
MoS prepared by the invention 2 The AIZS/fCDs photocatalyst is in the shape that quantum dots are attached to nanoflower.
Another object of the present invention is to provide the MoS 2 The AIZS/fCDs photocatalyst is applied to photocatalytic hydrogen production.
Photocatalytic activity evaluation:
weigh 0.02g (MoS) 2 AIZS/fCDs) photocatalyst, 0.528g (L-ascorbic acid) hole sacrificial agent and 15ml distilled water are added into a photoreactor to be completely dissolved, and N is introduced at a high flow rate 2 The gas is exhausted after the gas in the reactor is exhausted; under magnetic stirring, turning on a white light LED lamp with power of 300W for illumination for 5 hours, and sampling and analyzing once every 1 hour; the hydrogen production rate is calculated.
The invention utilizes the high visible light response capability of Ag-In-Zn-S quantum dots, and adopts electron promoter (MoS) 2 ) And hole promoters (fCDs) respectively accelerate the extraction of electrons and holes, greatly reduce the charge recombination probability, realize high-efficiency charge separation and improve the hydrogen production efficiency by photolysis of water. MoS (MoS) 2 Is nano flower, AIZS quantum dot and fCDs can be uniformly loaded on MoS 2 To immobilize the composite photocatalyst and effectively increase the catalytic active sites.
Advantageous effects
The invention has simple process, low cost and easy obtainment, is convenient for mass production, is nontoxic and harmless, and meets the requirement of environmental protectionAnd (5) solving. Realize that in MoS 2 Under the modification of the fCDs double-promoter, an electron-hole synergistic effect is formed to improve the charge separation efficiency and the photocatalysis is used for the research of high-efficiency hydrogen production. Under the excitation of visible light, the photo-generated holes and electrons are respectively and rapidly transferred to MoS 2 And on fCDs, the occurrence of recombination is greatly reduced, so that more electrons can be used for hydrogen production reaction, and the photocatalytic performance is improved.
Drawings
FIG. 1 MoS 2 /AIZS/fCDs、MoS 2 And XRD diffractograms of the AIZS photocatalyst;
FIG. 2 MoS 2 /AIZS/fCDs、AIZS/fCDs、AIZS/MoS 2 And ultraviolet-visible light absorption diagram (a) and photoluminescence diagram (b) of the AIZS photocatalyst;
FIG. 3 MoS 2 Transmission diagram of AIZS/fCDs;
FIG. 4 MoS 2 /AIZS/fCDs、AIZS/fCDs、AIZS/MoS 2 And photo-catalytic hydrogen production curve (a) and hydrogen production rate graph (b) of AIZS;
FIG. 5 MoS 2 /AIZS/fCDs、AIZS/fCDs、AIZS/MoS 2 And electrochemical impedance diagram of AIZS.
Detailed Description
The present invention will be described in detail with reference to the following examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples.
The preparation method of the fCDs precursor comprises the following steps: dissolving carbon quantum dots (CDs) and FcA in dimethyl sulfoxide, carrying out solvothermal reaction for 2-4 hours at 110-140 ℃ and preferably at 140 ℃ until the volume reaches 20mL, centrifuging and washing to obtain the carbon quantum dots (CDs): fcA mass volume ratio is 3-15 mg:0.48 to 2.4mg, preferably 12mg:1.92mg.
The MoS of the invention 2 The preparation method of the precursor comprises the following steps: 1mmol (NH) 4 ) 6 Mo 7 O 24 4H 2 O and 30mmol of CH 4 N 2 S is dissolved in 35mL deionized water, stirred vigorously for 20min to form a uniform solution, put into a stainless steel high-pressure vessel with 50mL Teflon lining, and subjected to hydrothermal reaction at 160-240 ℃ for 12-24 h, preferably 220 DEG CReacting for 18h, washing with 0.1M HCl to completely remove NH 4 + Drying at 60 deg.C under vacuum.
Example 1
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.34mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 3.48mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 5.1mmol/g/h.
Example 2
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.34mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 6.96mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 5.8mmol/g/h.
Example 3
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.34mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 10.44mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 6.3mmol/g/h.
Example 4
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.34mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 8.2mmol/g/h.
Example 5
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.34mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 17.4mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 5.4mmol/g/h.
Example 6
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.17mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 4.2mmol/g/h.
Example 7
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs)The method comprises the following steps:
A. 0.51mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 7.1mmol/g/h.
Example 8
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.51mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 0.8mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 1.4mmol/g/h.
Example 9
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.51mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 1.6mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 3.8mmol/g/h.
Example 10
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.51mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 2.4mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 6.4mmol/g/h.
Example 11
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.51mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs prepared were removed with 3mg of MoS 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 4.1mmol/g/h.
Example 12
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.51mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 6mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 6.4mmol/g/h.
Example 13
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.51mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 9mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 8.2mmol/g/h.
Example 14
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.51mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs prepared and 12mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 7.0mmol/g/h.
Example 15
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.51mmol of silver nitrate, 1.7mmol of indium nitrate, 0.85mmol of zinc acetate dihydrate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs thus prepared and 15mg of MoS were removed 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 4.2mmol/g/h.
Example 16
MoS (MoS) 2 Ag-In-Zn-S quantum dot co-modified with hole extraction functionalized carbon quantum dot (MoS) 2 AIZS/fCDs), comprising:
A. 0.51mmol of silver sulfate, 1.7mmol of indium sulfate, 0.85mmol of zinc sulfate and 5mmol of L-cysteine are weighed and dissolved in 5.5mL of water, and the pH value is adjusted to 8.5 by using a 1M NaOH solution;
B. continuously adding 13.92mmol fCDs precursor and 3.2mmol thioacetamide into the solution, uniformly stirring by ultrasonic, performing hydrothermal reaction for 4 hours at 110 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs;
C. 100mg of the AIZS/fCDs prepared were removed with 3mg of MoS 2 Dissolving in 10mL water, mechanically stirring for 12h, centrifuging, and washing to obtain MoS 2 /AIZS/fCDs。
Photocatalytic activity evaluation of photocatalyst: calculated, moS produced in this example 2 The hydrogen production rate per AIZS/fCDs was 7.9mmol/g/h.
FIG. 1 MoS 2 /AIZS/fCDs、MoS 2 And XRD diffractograms of the AIZS photocatalyst; as can be seen from XRD diffraction patterns when MoS 2 At a mass fraction of 9%, no MoS was present 2 But when the mass fraction reaches 13%, obvious MoS appears 2 Diffraction peaks, thereby explaining MoS 2 MoS of AIZS/fCDs 2 Is successfully compounded; and the diffraction peak of AIZS is also in MoS 2 Appears in AIZS/fCDs, demonstrating successful synthesis of the composite.
FIG. 2 MoS 2 /AIZS/fCDs、AIZS/fCDs、AIZS/MoS 2 And ultraviolet-visible light absorption diagram (a) and photoluminescence diagram (b) of the AIZS photocatalyst; as can be seen from fig. 2aAIZS is loaded with MoS 2 After fCDs, the light absorption intensity is obviously improved, and the improvement is carried out on MoS 2 and/AIZS/fCDs. In fig. 2b, the lower the photoluminescence intensity indicates a better separation efficiency. It can be seen that MoS 2 The strength of AIZS/fCDs is lower than that of the material, indicating MoS 2 AIZS/fCDs have better separation efficiency than other materials.
FIG. 3 MoS 2 Transmission diagram of AIZS/fCDs; from FIG. 3, moS is seen 2 The presence of composite material, but due to MoS 2 The coverage of (2) does not allow for a clear view of the appearance of quantum dots.
FIG. 4 MoS 2 /AIZS/fCDs、AIZS/fCDs、AIZS/MoS 2 And photo-catalytic hydrogen production curve (a) and hydrogen production rate graph (b) of AIZS; as seen in FIG. 4, moS 2 The hydrogen production rate of/AIZS/fCDs reaches 8.2mmol g -1 h -1 Is 20.5 times of pure AIZS quantum dot, 5.7 times of AIZS-fCDs and AIZS-MoS 2 Is 6.5 times as large as the above. Demonstration of MoS 2 Plays a role in effectively promoting charge separation with fCDs.
FIG. 5 MoS 2 /AIZS/fCDs、AIZS/fCDs、AIZS/MoS 2 And electrochemical impedance diagram of AIZS. The radius of the electrochemical impedance represents the separation efficiency of the sample charge, and MoS is seen from the figure 2 The radius of AIZS/fCDs is much smaller than that of the remaining material, and MoS is explained on the other hand 2 The charge separation efficiency of/AIZS/fCDs is the best.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (10)
1.MoS (MoS) 2 The preparation method of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dot is characterized by comprising the following steps:
A. dissolving silver nitrate, indium nitrate, zinc acetate and L-cysteine in water, and adjusting the pH value to 8.5 by using a 1M NaOH solution, wherein the silver nitrate is prepared by the following steps: indium nitrate: zinc acetate: l-cysteine: the molar volume ratio of water is 0.17-0.51 mmol:0.17 to 1.7mmol:0.17 to 0.85mmol:5mmol:5.5mL;
B. continuously adding fCDs precursor and thioacetamide into the solution, stirring uniformly by ultrasonic, performing hydrothermal reaction for 2-4 hours at 110-140 ℃, cooling to room temperature, and centrifuging and washing to obtain AIZS/fCDs, wherein the fCDs precursor is prepared by the steps of: thioacetamide: the molar volume ratio of water is 3.48-17.4 mmol:0.4 to 3.2mmol:5.5mL of water in step A; the preparation method of the fCDs precursor comprises the following steps: dissolving carbon quantum dots CDs and ferrocenecarboxylic acid FcA in dimethyl sulfoxide, carrying out solvothermal reaction for 2-4 hours at the temperature of 110-140 ℃ until the volume reaches 20mL, centrifuging and washing to obtain the carbon quantum dots CDs, wherein the carbon quantum dots CDs are prepared by the steps of: fcA mass ratio is 3-15 mg: 0.48-2.4 mg;
C. mixing the prepared AIZS/fCDs with MoS 2 Dissolving the precursor in water, mechanically stirring for 8-16 h, centrifuging and washing to obtain MoS 2 AIZS/fCDs, wherein the AIZS/fCDs: moS (MoS) 2 Precursor: the mass volume ratio of water is 100mg: 3-15 mg:10mL; the MoS 2 The precursor is prepared by the following steps: 1mmol (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O and 30mmol of CH 4 N 2 S is dissolved in 35mL deionized water, stirred vigorously for 20min to form a uniform solution, put into a stainless steel high-pressure device with 50mL Teflon lining, subjected to hydrothermal reaction at 160-240 ℃ for 12-24 h, and washed with 0.1M HCl to completely remove NH 4 + Drying at 60deg.C under vacuum to obtain the final product.
2. The MoS of claim 1 2 The preparation method of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dot is characterized by comprising the following steps of: step A, silver nitrate: indium nitrate: zinc acetate: l-cysteine: the molar volume ratio of water was 0.34mmol:1.7mmol:0.85mmol:5mmol:5.5mL.
3. The MoS of claim 1 2 The preparation method of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dot is characterized by comprising the following steps of: and B, continuously adding the fCDs precursor and thioacetamide into the solution, stirring uniformly by ultrasonic, and performing hydrothermal reaction for 4 hours at 110 ℃.
4. The MoS of claim 1 2 The preparation method of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dot is characterized by comprising the following steps of: the fdds precursor of step B: thioacetamide: the molar volume ratio of water was 14mmol:3.2mmol:5.5mL.
5. The MoS of claim 1 2 The preparation method of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dot is characterized by comprising the following steps of: and B, dissolving the carbon quantum dots CDs and ferrocenecarboxylic acid FcA in dimethyl sulfoxide, fixing the volume to 20mL, performing solvothermal reaction for 4 hours at 140 ℃, centrifuging, and washing to obtain the carbon quantum dots CDs: fcA the mass ratio is 12mg:1.92mg.
6. The MoS of claim 1 2 The preparation method of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dot is characterized by comprising the following steps of: step C, the prepared AIZS/fCDs is combined with MoS 2 The precursor is dissolved in water and mechanically stirred for 12h.
7. The MoS of claim 1 2 The preparation method of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dot is characterized by comprising the following steps of: step C, AIZS/fCDs: moS (MoS) 2 Precursor: the mass volume ratio of the water is 100mg:9mg:10 And (3) mL.
8. The MoS of claim 1 2 The preparation method of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dot is characterized by comprising the following steps of: 1mmol (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O and 30mmol of CH 4 N 2 S is dissolved in 35mL deionized water, stirred vigorously for 20min to form a uniform solution, put into a stainless steel high-pressure vessel lined with Teflon of 50mL, reacted hydrothermally at 220 ℃ for 18h, and washed with 0.1M HClTotal NH removal 4 + Drying at 60deg.C under vacuum to obtain the final product.
9. MoS made according to any one of claims 1-8 2 And the Ag-In-Zn-S quantum dots are co-modified with the hole extraction functionalized carbon quantum dots.
10. A MoS as claimed in claim 9 2 The application of the Ag-In-Zn-S quantum dot co-modified with the hole extraction functionalized carbon quantum dot is characterized In that: the method is applied to photocatalytic hydrogen production.
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