CN105964276A - Carbon quantum dot-loaded SnS2 nanometer sheet and its preparation method and use - Google Patents
Carbon quantum dot-loaded SnS2 nanometer sheet and its preparation method and use Download PDFInfo
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- CN105964276A CN105964276A CN201610293108.3A CN201610293108A CN105964276A CN 105964276 A CN105964276 A CN 105964276A CN 201610293108 A CN201610293108 A CN 201610293108A CN 105964276 A CN105964276 A CN 105964276A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 238000001704 evaporation Methods 0.000 claims description 24
- 230000008020 evaporation Effects 0.000 claims description 24
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 235000014121 butter Nutrition 0.000 claims description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000003708 ampul Substances 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002096 quantum dot Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
Abstract
The invention relates to a carbon quantum dot-loaded SnS2 nanometer sheet and its preparation method and use and belongs to the technical field of inorganic semiconductor nano-materials. The preparation method comprises immersing SnS2 nanometer sheets in a carbon source solution and carrying out pyrolysis to produce carbon quantum dots on the SnS2 nanometer sheet surfaces so that the carbon quantum dot-loaded SnS2 nanometer sheets are obtained, wherein the carbon quantum dot-loaded SnS2 nanometer sheets are crosslinked to form a nanometer wall. The carbon quantum dot has the size of 5-20nm. The carbon quantum dot adhesion method prevents oxidation corrosion in photocatalytic water splitting and improves catalyst efficiency. KIO3 is used as a sacrificial agent and an oxygen production rate is 1.1mmol/g.h. The preparation method has the advantages of simple processes, operation convenience, fast rate and environmental friendliness. The preparation method does not use and produce toxic and corrosive gas and has a wide application prospect.
Description
Technical field
The invention belongs to semiconductor nano material technical field, relate to the SnS of a kind of carbon quantum dot load2Nanometer
Sheet, its preparation method and application, particularly relate to the SnS of a kind of carbon quantum dot load2Nanometer sheet, its preparation side
Method and the application in photocatalytic water oxygen field.
Background technology
Water is rich in natural resources on the earth, faces today that energy crisis environmental pollution is the most serious, finds
New clean energy resource becomes the mankind and compels problem to be solved.Wherein, Hydrogen Energy is the most attractive candidate, because of
Its calorific value is high and combustion product is water.Since finding to utilize decomposing water with solar energy by catalyst,
People have put into keen interest to it and have deeply studied widely, and various catalyst are developed, including
Oxide, sulfide, some salts etc..
The IV-VI compound of binary is because of the physics of its uniqueness and chemical property, at photoelectricity, thermoelectricity and battery etc.
Field has potential application prospect.Wherein stannic disulfide (SnS2) owing to it is easily prepared, environmental friendliness
And chemically stable, cause the research interest of substantial amounts of scientist.Its suitable band structure
(Eg～2.3eV, Ecb～-0.1eV, Evb～2.2eV, Vs NHE) makes it can effectively absorb solar energy, produces
Raw stronger photoelectric current, and the photocatalysis Decomposition of water, oxygen the most processed can be used for.
But, as the SnS of sulfide2, during photolysis water, the most oxidized corrosion, destroys knot
Structure, thus lose its catalytic performance.Prior art carries out spreadability protection by employing to catalyst hinder
Oxidation is corroded, and such as so that it is surface oxidation, generates one layer of SnO2；Or use rGO (reduction-oxidation
Graphene) wrap up.But this had the most both blocked luminous energy, affected opto-electronic conversion, completely cut off again catalyst
With contacting of water, cause catalyst ineffective.
Thus, it is necessary to develop a kind of novel sulfide SnS2Or complex so that it is not only there is antioxidation
Corrosion feature, there is again excellent catalytic performance and photoelectric transformation efficiency, this be one challenging
A difficult problem.
Summary of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of carbon quantum dot and bear
The SnS carried2Nanometer sheet, its preparation method and the application in photocatalytic water oxygen field.The carbon quantum dot of the present invention
The SnS of load2Nanometer sheet not only avoid the oxide etch during photocatalytic water, improves again catalyst
Efficiency, with KIO3For sacrifice agent, oxygen speed processed reaches 1.1mmol/g h；And, side of the present invention
Method has that synthesis step is simple, speed fast, morphology controllable and the advantage of environmental protection, has wide application
Prospect.
For reaching above-mentioned purpose, the present invention by the following technical solutions:
First aspect, the present invention provides the SnS that a kind of carbon quantum dot loads2Nanometer sheet, described carbon quantum dot is born
The SnS carried2Nanometer sheet includes: SnS2Nanometer sheet and be supported on SnS2The carbon quantum dot on nanometer sheet surface.
Preferably, the SnS of described carbon quantum dot load2Nanometer sheet vertical-growth is in substrate.
Preferably, described substrate is that FTO glass, carbon cloth, evaporation have the FTO glass of metal level or evaporation to have
Any one or the combination of at least two in the carbon cloth of metal level, but it is not limited to the above-mentioned substrate enumerated,
Other substrates that can reach same effect are used equally to the present invention, and being preferably evaporation has the FTO glass of metal level
Glass.
Preferably, described evaporation has in the FTO glass of metal level, and metal level is Ni layer, Cr layer, Ti layer
Or any one or the combination of at least two in Au layer.
Preferably, the SnS of described carbon quantum dot load2Nm wall, described nm wall is got in touch with between nanometer sheet
Highly preferred be 500～1000nm, can be such as 500nm, 520nm, 550nm, 575nm,
600nm, 650nm, 680nm, 700nm, 750nm, 800nm, 900nm or 1000nm, further
It is preferably 500nm.
Preferably, described SnS2The thickness of nanometer sheet is 5～30nm, can be such as 5nm, 6nm, 7nm,
8nm, 10nm, 12nm, 14nm, 15nm, 17nm, 20nm, 23nm, 25nm or 30nm etc..
Preferably, the particle diameter of described carbon quantum dot is 5～20nm, can be such as 5nm, 6nm, 7nm,
8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 15nm, 18nm or 20nm etc..
Second aspect, the present invention provides the SnS of carbon quantum dot load as described in relation to the first aspect2The system of nanometer sheet
Preparation Method, said method comprising the steps of:
By SnS2Nanometer sheet immerses in the solution of carbon source, takes out, is then placed in reacting furnace, heating, carries out true
Empty annealing, obtains the SnS of carbon quantum dot load2Nanometer sheet.
Preferably, in the solution of described carbon source, carbon source is in glucose, sucrose, maltose or glyceraldehyde
Any one or the mixture of at least two.
Preferably, in the solution of described carbon source, the concentration of carbon source is 0.4～1.5M, can be such as 0.4M,
0.5M, 0.6M, 0.8M, 1M, 1.2M or 1.5M etc., preferably 0.5M.
Preferably, in the solution of described carbon source, solvent is the mixture of second alcohol and water, ethanol in described solvent
It is preferably (1～3) with the volume ratio of water: 1, such as, can be 1:1,1.2:1,1.5:1,2:1,2.3:1,2.5:1
Or 3:1 etc., more preferably 1:1.
Preferably, the time of described immersion is 2～5h, can be such as 2h, 2.5h, 3h, 3.2h, 3.6h,
4h, 4.5h or 5h etc., preferably 4h, if the time immersed is less than 2h, the time of chemisorbed is shorter,
It is unfavorable for carbon source molecule being uniformly distributed at sample surfaces；If the immersion time is longer than 5h, chemisorbed reaches
Balance, carbon source molecule sample surfaces distribution uniformly, no longer change over, the prolongation time can lead
Cause production cycle prolongation, therefore, consider the effect after immersion processes and time cost, be preferably immersed in
Time be 2～5h.
Preferably, the temperature of described heating is 450～550 DEG C, can be such as 450 DEG C, 460 DEG C, 475 DEG C,
480 DEG C, 490 DEG C, 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C or 550 DEG C etc..
Preferably, the time of described vacuum annealing is 1～3h, can be such as 1h, 1.2h, 1.4h, 1.5h,
1.7h, 1.9h, 2h, 2.3h, 2.5h or 3h etc..
Preferably, described reacting furnace is pipe reaction stove.
Preferably, after vacuum annealing completes, naturally cool to room temperature.
Preferably, before described method is additionally included in vacuum annealing, it is carried out the step of quartz ampoule.
Preferably, in the step of described cleaning quartz ampoule, Ar is used to be carried out.
As the optimal technical scheme of the method for the invention, described SnS2The preparation method of nanometer sheet is as follows:
Substrate is inserted in the ethanol solution of butter of tin and thioacetamide, carry out hydro-thermal in 60～80 DEG C anti-
Should, obtain the SnS being grown on FTO glass2Nanometer sheet.
In this optimal technical scheme, the temperature of hydro-thermal reaction is 60～80 DEG C, can be such as 60 DEG C, 62 DEG C,
65 DEG C, 68 DEG C, 70 DEG C, 75 DEG C or 80 DEG C etc..
Preferably, described substrate is that FTO glass, carbon cloth, evaporation have the FTO glass of metal level or evaporation to have
Any one or the combination of at least two in the carbon cloth of metal level, but it is not limited to the above-mentioned substrate enumerated,
Other substrates that can reach same effect are used equally to the present invention, and being preferably evaporation has the FTO glass of metal level
Glass, it is preferred to use evaporation has the FTO of metal level to have two aspects as the reason of substrate: one is evaporated metal layer
Be conducive to improving the SnS that the carbon quantum dot of substrate and its upper growth loads2The adhesiveness of nanometer sheet；Two is evaporation
Metal level is conducive to improving the suprabasil carbon quantum dot that is grown in prepared and loads SnS2The electronics of nanometer sheet
Conductivity.
Preferably, described evaporation has in the FTO glass of metal level, and metal level is Ni layer, Cr layer, Ti layer
Or any one or the combination of at least two in Au layer, but it is not limited to the above-mentioned metal level enumerated, its
He can reach the metal level of same effect and is used equally to the present invention.
Preferably, it is preferable that in the ethanol solution of described butter of tin and thioacetamide, butter of tin
Concentration is 15～35mM, preferably 20mM.
Preferably, in the ethanol solution of described butter of tin and thioacetamide, the concentration of thioacetamide is
50～80mM, preferably 60mM.
Preferably, the time of described hydro-thermal reaction is 6～12h, can be such as 6h, 7h, 8.5h, 9h,
10h, 11h or 12h etc..
Preferably, described method is additionally included in after hydro-thermal reaction terminates, and carries out the step washed and be dried.
As the further preferred technical scheme of the method for the invention, a kind of carbon amounts as described in relation to the first aspect
The SnS of son point load2The preparation method of nanometer sheet, said method comprising the steps of:
(1) FTO glass is inserted the butter of tin containing 20mM, and the thioacetamide of 60mM
In ethanol solution, in 60～80 DEG C of hydro-thermal reactions 6～12h, wash and be dried, obtain being grown on FTO glass
On SnS2Nanometer sheet；
(2) SnS being grown on FTO glass that step (1) is obtained2Nanometer sheet immerses the Portugal of 0.5M
Grape sugar solution in 2～5h, take out, dry；
Wherein, the mixture of the second alcohol and water that solvent is volume ratio 1:1 in the solution of described glucose；
(3) growth that step (2) obtains there is SnS2The FTO glass of nanometer sheet is placed in pipe reaction stove
Center warm area, after cleaning quartz ampoule with Ar, is increased to 300～500 DEG C by furnace temperature, and vacuum annealing 1～3h is cold
But, the SnS of carbon quantum dot load is obtained2Nanometer sheet.
The third aspect, the present invention provides the SnS of carbon quantum dot load as described in relation to the first aspect2Answering of nanometer sheet
With, the SnS of described carbon quantum dot load2Nanometer sheet is applied to photocatalytic water.
Compared with the prior art, there is advantages that
(1) SnS of the carbon quantum dot load of the present invention2In nanometer sheet, SnS2The area load of nanometer sheet has
Carbon quantum dot (the SnS of described carbon quantum dot load2The structural representation of nanometer sheet sees Fig. 4), surface
The introducing of carbon quantum dot not only avoid the oxide etch during photocatalytic water, but also improves catalyst effect
Rate, with KIO3For sacrifice agent, oxygen speed processed reaches 1.1mmol/g h.
(2) the method for the invention is by SnS2Nanometer sheet immerses in the solution of carbon source, then carries out Pintsch process
Method makes carbon source decomposition obtain carbon quantum dot and load to SnS2The surface of nanometer sheet, described method has preparation work
Skill is simple and convenient to operate, speed is fast, morphology controllable and the advantage of environmental protection, in preparation process not
Use and also will not produce toxicity or corrosive gas, have broad application prospects.
Accompanying drawing explanation
Fig. 1 a is the SnS of comparative example 12Scanning electron microscope (SEM) top view of nanometer sheet and side view
(illustration), Fig. 1 b is the C:SnS of embodiment 12Scanning electron microscope (SEM) top view of nanometer sheet
With partial enlarged drawing (illustration)；
Fig. 2 a is the C:SnS of embodiment 12Transmission electron microscope (TEM) figure of nanometer sheet, Fig. 2 a inserts
Figure is SEAD, and Fig. 2 b is the C:SnS of embodiment 12The high-resolution lattice fringe figure of nanometer sheet；
Fig. 3 a is the C:SnS of embodiment 12Raman (Raman) analysis chart of nanometer sheet；Fig. 3 b is for implementing
The energy spectrum analysis figure of example 1；
Fig. 4 is the SnS of the carbon quantum dot load of the present invention2The structural representation of nanometer sheet；
Fig. 5 a and Fig. 5 b is the electro-chemical test (PEC) of different sample (F, FS, FNS and FNSC)
Analysis chart, wherein Fig. 5 a is I-T curve, and Fig. 5 b is EIS curve；
Fig. 6 a is the oxygen Performance comparision figure processed of different sample (FS, FNS and FNSC)；Fig. 6 b is FNSC
The oxidative stability test analysis figure processed of sample；
Note: the F in accompanying drawing represents FTO glass；FS represents being grown on FTO glass of comparative example 1
SnS2Nanometer sheet；What FNS represented comparative example 2 is grown on the suprabasil SnS of FTO-Ni2Nanometer sheet；FNSC
Represent embodiment 1 is grown on the suprabasil C:SnS of FTO-Ni2Nanometer sheet.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
Embodiment 1
The SnS of carbon quantum dot load2Nanometer sheet (C:SnS2Nanometer sheet) preparation:
(1) by clean FTO glass surface evaporation layer of Ni, then evaporation is had the FTO of W metal layer
Glass, as substrate (this substrate named FTO-Ni substrate), inserts the butter of tin (SnCl containing 20mM4)
And the thioacetamide (CH of 60mM3CSNH2) ethanol solution in, 70 DEG C of hydro-thermal reactions, growth
6h, washing, it is dried, obtaining growth has SnS2The substrate of nanometer sheet.
(2) glucose solution (ethanol and water ratio 1:1) of configuration 0.5M, by (1) step gained
Growth has SnS24h in solution is immersed in the substrate of nanometer sheet, takes out, dries, be subsequently placed in pipe reaction stove
Center warm area, after cleaning quartz ampoule with Ar, is increased to 500 DEG C by furnace temperature, the coldest after vacuum annealing 1.5h
But to room temperature, the SnS of carbon quantum dot load is obtained2Nanometer sheet, named C:SnS2Nanometer sheet.
Its performance indications are briefly illustrated with lower part:
Fig. 1 a is the SnS of comparative example 12Scanning electron microscope (SEM) top view of nanometer sheet and side view
(illustration), Fig. 1 b is the C:SnS of embodiment 12Scanning electron microscope (SEM) top view of nanometer sheet
With partial enlarged drawing (illustration), from Fig. 1 a and Fig. 1 b, SnS2Nanometer sheet vertical-growth in substrate,
Contact reticulates, highly 500nm, and thickness is 5～30nm, and C lateral size of dots 10nm is evenly distributed
In nanometer sheet.
Fig. 2 a is the C:SnS of embodiment 12Transmission electron microscope (TEM) figure of nanometer sheet, Fig. 2 a inserts
Figure is SEAD, and Fig. 2 b is the C:SnS of embodiment 12The high-resolution lattice fringe figure of nanometer sheet, by
Fig. 2 a and Fig. 2 b understands, and C quantum dot is distributed in SnS2In nanometer sheet, interior in SEAD
Outer two set annulus show, both polycrystalline, wherein, internal ring is C quantum dot, outer shroud is SnS2；High
Resolution lattice bar graph is it will be clear that C (0.34nm) and SnS2(0.29nm) lattice.
Fig. 3 a is C:SnS2Raman (Raman) analysis chart of nanometer sheet, from the table of Fig. 3 a, C quantum dot
Face is rendered as unformed shape.Fig. 3 b is C:SnS2The energy spectrum analysis figure of nanometer sheet, from Fig. 3 b, this reality
Execute the C:SnS that example prepares2Nanometer sheet comprises C, S and Sn element, and the weight percentage of each element is
7.47%, 33.83% and 58.70%；The atomic percentage conc of each element is 28.63%, 48.60% and
22.78%.
Fig. 5 a and Fig. 5 b reflects its PhotoelectrochemicalProperties Properties, and 5a is density of photocurrent (I-T over time
Figure), On represents and turns on light, and Off represents and turns off the light, it can be seen that after load C quantum dot, photoelectric current
Density adds one times, from 18.8 original μ A/cm2, to 38.6 μ A/cm2；4b is electrochemical impedance spectroscopy
(EIS), reflection material conductivity and separation of charge efficiency, it can be seen that the load of C quantum dot makes material
Electric conductivity and the separation of charge efficiency of material have promoted.
Fig. 6 a and Fig. 6 b is catalyst oxygen Performance comparision, it can be seen that the load of C quantum dot not only makes
SnS2Catalyst stability promotes, it is to avoid oxide etch, and enhances the performance of catalyst, successfully
The difficult problem proposed on solving.
Embodiment 2
Except there being the FTO glass of W metal layer as the evaporation in substrate alternative embodiment 1 with FTO glass
Outside substrate, other preparation methoies and condition are same as in Example 1, the SnS being grown on matrix obtained2Receive
Rice sheet.
The SnS of the carbon quantum dot load that the present embodiment prepares2Nanometer sheet vertical-growth, in substrate, is got in touch with
Reticulate, highly 500nm, C lateral size of dots 10nm, be evenly distributed in nanometer sheet；C and SnS2
All having polycrystalline particle to constitute, the surface of C quantum dot is rendered as unformed shape；Photoelectrochemical experiments shows, light
Electric current density is up to 27 μ A/cm2, to test through more than 3 hours and also do not come off, corrosion resistance is good.
The present embodiment 2 and embodiment 1 are carrying out photoelectrochemical experiments contrast, and result display embodiment 1 is to steam
Be coated with the FTO glass of W metal layer as substrate compared to FTO glass as substrate, the knot of its nanometer sheet
Conjunction is more preferable, nanometer sheet difficult drop-off.
Embodiment 3
(1) by clean FTO glass surface evaporation layer of Ni, then evaporation is had the FTO of W metal layer
Glass, as substrate, inserts the butter of tin (SnCl containing 15mM4) and the thioacetamide of 50mM
(CH3CSNH2) ethanol solution in, 60 DEG C of hydro-thermal reactions, grow 12h, washing, be dried, given birth to
Long have SnS2The substrate of nanometer sheet.
(2) glucose solution (ethanol and water ratio 3:1) of configuration 1.5M, by (1) step gained
Growth has SnS23h in solution is immersed in the substrate of nanometer sheet, takes out, dries, be subsequently placed in pipe reaction stove
Center warm area, after cleaning quartz ampoule with Ar, is increased to 530 DEG C, natural cooling after vacuum annealing 3h by furnace temperature
To room temperature, obtain the SnS of carbon quantum dot load2Nanometer sheet, named C:SnS2Nanometer sheet.
The SnS of the carbon quantum dot load that the present embodiment prepares2Nanometer sheet vertical-growth, in substrate, is got in touch with
Reticulating, highly 500nm, photoelectrochemical experiments shows, density of photocurrent is 29～35 μ A/cm2, through 3
Within more than individual hour, testing and also do not come off, corrosion resistance is good.
Embodiment 4
(1) by clean FTO glass surface one layer of Cr of evaporation, then evaporation is had the FTO of metal Cr layer
Glass, as substrate (this substrate named FTO-Cr substrate), inserts the butter of tin (SnCl containing 35mM4)
And the thioacetamide (CH of 80mM3CSNH2) ethanol solution in, 80 DEG C of hydro-thermal reactions, growth
6h, washing, it is dried, obtaining growth has SnS2The substrate of nanometer sheet.
(2) glucose solution (ethanol and water ratio 2:1) of configuration 0.4M, by (1) step gained
Growth has SnS25h in solution is immersed in the substrate of nanometer sheet, takes out, dries, be subsequently placed in pipe reaction stove
Center warm area, after cleaning quartz ampoule with Ar, is increased to 500 DEG C, natural cooling after vacuum annealing 1h by furnace temperature
To room temperature, obtain the SnS of carbon quantum dot load2Nanometer sheet, named C:SnS2Nanometer sheet.
The SnS of the carbon quantum dot load that the present embodiment prepares2Nanometer sheet vertical-growth, in substrate, is got in touch with
Reticulate, highly 500nm, thickness 5～30nm, C lateral size of dots 5～20nm, be evenly distributed in and receive
On rice sheet；C and SnS2All having polycrystalline particle to constitute, the surface of C quantum dot is rendered as unformed shape；Photoelectricity
Chemical experiment shows, density of photocurrent is stable at 30～40 μ A/cm2。
Comparative example 1
The method preparation using prior art is grown on the SnS on FTO glass2Nanometer sheet, named FS,
Growing method sees the document Revisiting Metal Sulfide Semiconductors:A of Shinde D V et al.
Solution‐Based General Protocol for Thin Film Formation,Hall Effect
Measurement,and Application Prospects(Advanced Functional Materials,2015,
25 (36), 5739-5747).
The SnS that this comparative example prepares2Nanometer sheet vertical-growth is in substrate, and height is 300～500nm,
Thickness is 50～100nm, is distributed sparse, and easily comes off, and oxygen speed processed is 0.15mmol/g/h, and
After 3 hours, owing to coming off of photochemical corrosion and nanometer sheet, the most no oxygen separate out.
Comparative example 2
In addition to not comprising step (2), other preparation methoies and condition are same as in Example 1.
The SnS that this comparative example prepares2Nanometer sheet vertical-growth is in substrate, and contact reticulates, highly
500～1000nm, thickness is 5～30nm, and oxygen speed processed is 0.7mmol/g/h, after 3 hours, due to
Coming off of photochemical corrosion and nanometer sheet, oxygen evolution is the slowest, until no oxygen produces.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention
It is not limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed ability real
Execute.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to product of the present invention
The equivalence of each raw material is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the guarantor of the present invention
Within the scope of protecting scope and disclosure.
Claims (10)
1. the SnS of a carbon quantum dot load2Nanometer sheet, it is characterised in that include SnS2Nanometer sheet and
It is supported on SnS2The carbon quantum dot on nanometer sheet surface.
The SnS of carbon quantum dot the most according to claim 1 load2Nanometer sheet, it is characterised in that institute
State the SnS of carbon quantum dot load2Nanometer sheet vertical-growth is in substrate；
Preferably, described substrate is FTO glass or the evaporation that FTO glass, carbon cloth, evaporation have metal level
Having any one or the combination of at least two in the carbon cloth of metal level, being preferably evaporation has the FTO of metal level
Glass；
Preferably, described evaporation has in the FTO glass of metal level, and metal level is Ni layer, Cr layer, Ti layer
Or any one or the combination of at least two in Au layer；
Preferably, the SnS of described carbon quantum dot load2Nm wall, described nm wall is got in touch with between nanometer sheet
Highly preferred be 500～1000nm, more preferably 500nm；
Preferably, described SnS2The thickness of nanometer sheet is 5～30nm；
Preferably, the particle diameter of described carbon quantum dot is 5～20nm.
3. the SnS of carbon quantum dot load as claimed in claim 1 or 22The preparation method of nanometer sheet, its
It is characterised by, said method comprising the steps of:
By SnS2Nanometer sheet immerses in the solution of carbon source, takes out, is then placed in reacting furnace, heating, carries out true
Empty annealing, obtains the SnS of carbon quantum dot load2Nanometer sheet.
Method the most according to claim 3, it is characterised in that in the solution of described carbon source, carbon source
For any one in glucose, sucrose, maltose or glyceraldehyde or the mixture of at least two；
Preferably, in the solution of described carbon source, the concentration of carbon source is 0.4～1.5M, preferably 0.5M.
5. according to the method described in claim 3 or 4, it is characterised in that in the solution of described carbon source, molten
Agent is the mixture of second alcohol and water；
Preferably, in described solvent, the volume ratio of second alcohol and water is (1～3): 1, preferably 1:1.
6. according to the method described in any one of claim 3-5, it is characterised in that the time of described immersion is
2～5h, preferably 4h.
7. according to the method described in any one of claim 3-6, it is characterised in that the temperature of described heating is
450～550 DEG C；
Preferably, the time of described vacuum annealing is 1～3h；
Preferably, described reacting furnace is pipe reaction stove；
Preferably, before described method is additionally included in vacuum annealing, it is carried out the step of quartz ampoule；
Preferably, in the step of described cleaning quartz ampoule, Ar is used to be carried out.
8. according to the method described in any one of claim 3-7, it is characterised in that described SnS2Nanometer sheet
Preparation method as follows:
Substrate is inserted in the ethanol solution of butter of tin and thioacetamide, carry out hydro-thermal in 60～80 DEG C anti-
Should, obtain being grown on suprabasil SnS2Nanometer sheet；
Preferably, described substrate is FTO glass or the evaporation that FTO glass, carbon cloth, evaporation have metal level
There is any one or the combination of at least two in the carbon cloth of metal level；
Preferably, described evaporation has in the FTO glass of metal level, and metal level is Ni layer, Cr layer, Ti layer
Or any one or the combination of at least two in Au layer；
Preferably, in the ethanol solution of described butter of tin and thioacetamide, the concentration of butter of tin is
15～35mM, preferably 20mM；
Preferably, in the ethanol solution of described butter of tin and thioacetamide, the concentration of thioacetamide is
50～80mM, preferably 60mM；
Preferably, the time of described hydro-thermal reaction is 6～12h；
Preferably, described method is additionally included in after hydro-thermal reaction terminates, and carries out the step washed and be dried.
9. according to the method described in any one of claim 3-8, it is characterised in that described method includes following
Step:
(1) FTO glass is inserted the butter of tin containing 20mM, and the thioacetamide of 60mM
In ethanol solution, in 60～80 DEG C of hydro-thermal reactions 6～12h, wash, be dried, obtain being grown in FTO glass
On SnS2Nanometer sheet；
(2) SnS being grown on FTO glass that step (1) is obtained2Nanometer sheet immerses the Portugal of 0.5M
Grape sugar solution in 2～5h, take out, dry；
Wherein, the mixture of the second alcohol and water that solvent is volume ratio 1:1 in the solution of described glucose；
(3) growth that step (2) obtains there is SnS2The FTO glass of nanometer sheet is placed in pipe reaction stove
Center warm area, after cleaning quartz ampoule with Ar, is increased to 300～500 DEG C by furnace temperature, and vacuum annealing 1～3h is cold
But, the SnS of carbon quantum dot load is obtained2Nanometer sheet.
10. the SnS of carbon quantum dot load as claimed in claim 1 or 22The application of nanometer sheet, its feature
It is, the SnS of described carbon quantum dot load2Nanometer sheet is applied to photocatalytic water.
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| CN109244422A (en) * | 2018-10-19 | 2019-01-18 | 中国矿业大学 | A kind of lithium ion battery SnS/ carbon quantum dot/graphene composite negative and preparation method |
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