CN106238089A - A kind of visible light-responded g C3n4/ SnS2the preparation method of composite photo-catalyst - Google Patents
A kind of visible light-responded g C3n4/ SnS2the preparation method of composite photo-catalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000005253 cladding Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002242 deionisation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention newly discloses a kind of visible light-responded g C3N4/SnS2The preparation method of composite photo-catalyst, the preparation process of the present invention is as follows: (1) Hydrothermal Synthesis SnS2；(2) thermal polymerization prepares g C3N4, grind into powder is standby；(3) Vacuum-assisted method g C3N4/SnS2, the g C prepared by step (2) will be added3N4.Wherein, in step (3), synthesize SnS2Raw material include the SnCl of 5mmol4.5H2The C of O and 10mmol2H5NS, at synthesis g C3N4/SnS2During composite photo-catalyst, add described g C3N4Quality be the SnS that step (1) generates225% the 100% of quality, wherein best in quality is SnS2The 66.7% of quality.The g C that the present invention prepares3N4/SnS2Nano combined photocatalyst has more advantage, it be possible not only to suppress electronics (e) hole (h+) to compound, but also further increase the percent reduction to chromate waste water, the more important thing is can expensive metallic element in substituted metal semi-conducting material, reduce cost and there is good stability, easily realizing large-scale production.
Description
Technical field
The present invention relates to the preparation method of a kind of catalyst, particularly relate to a kind of visible light-responded g-C3N4/SnS2Complex light
The preparation method of catalyst.
Background technology
At present, g-C in recent years3N4As novel nonmetal organic semiconducting materials, due to the narrower (E of its band gapg=
2.7eV), at room temperature to visible light-responded, the most antiacid, the corrosion of alkali, light, there is good stability and easy modification etc. excellent
Point, causes the extensive concern of people.But due to g-C3N4The reasons such as electron-hole recombinations is fast and specific surface area is the biggest, urge at light
The practical application effect that change processes water pollutant is unsatisfactory.SnS2It is visible ray semiconductor light-catalyst, has good light
Catalytic performance, but at high temperature there is stronger volatility and self there is photoetch, have a strong impact on SnS2Light-catalysed
Application prospect.Therefore the method for modifying seeking photocatalyst simple, efficient, high performance pushes away for Photocatalitic Technique of Semiconductor
Wide and application has great importance.
Table 1g-C3N4And SnS2The electrode potential that can carry
G-C is given from table 13N4And SnS2Conduction band and the electrode potential values of valence band can be seen that g-C3N4Conduction band and valency
The electrode potential of band is intended to compare SnS2Electrode potential more negative, according to can band matching theory, SnS2And g-C3N4There is the energy of coupling
Band structure.The present invention is in order to overcome SnS2And g-C3N4Both shortcomings, it is achieved have complementary advantages, use g-C3N4With SnS2Preparation g-
C3N4/SnS2Composite nano materials, improves g-C3N4With SnS2The separation efficiency of photo-generated carrier in nanoparticle, increases photoproduction electricity
In the life-span of lotus, promote its photocatalytic activity.
This g-C3N4/SnS2Nano combined photocatalyst has more advantage, and it is possible not only to inhibit electronics
(e-)-hole (h+) to compound, but also further increase the percent reduction to chromate waste water, it is often more important that can replace
Expensive metallic element in metal semiconductor material, reduces cost and has good stability.
Summary of the invention
The present invention provides expensive metallic element in a kind of substituted metal semi-conducting material, reduces cost and has
There is the g-C of good stability3N4/SnS2The preparation method of nano combined photocatalyst, it is proposed that following technical scheme:
A kind of visible light-responded g-C3N4/SnS2The preparation method of composite photo-catalyst, its preparation process is as follows:
(1) Hydrothermal Synthesis SnS2: take a certain amount of SnCl4.5H2O is put in reactor, and the citric acid adding 0.25mol/L is molten
Liquid, adds a certain amount of C after stirring and dissolving2H5NS, after continuing stirring a period of time, is placed in reactor in baking oven at 150 DEG C
Heating 12h；When system naturally cools to room temperature, obtained tan precipitate is carried out sucking filtration, through deionized water wash,
After air dry oven is dried 4h at 80 DEG C, it is ground to powder and weighs；
(2) thermal polymerization prepares g-C3N4: take a certain amount of CO (NH2)2Put in crucible, described crucible is being put into horse
Not in stove, after being warming up to 540 DEG C with the speed of 20 DEG C/min, persistently calcine 2h, during after naturally cool to room temperature, by obtained shallow
Yellow product carries out sucking filtration, through deionized water wash, after being dried 4h at 80 DEG C in air dry oven, is ground to powder and preserves
Standby；
(3) Vacuum-assisted method g-C3N4/SnS2: weigh a certain amount of SnCl4.5H2O is put in reactor, adds
0.25mol/L citric acid solution, adds a certain amount of C after stirring and dissolving2H5NS, after continuing stirring a period of time, weighs a certain amount of
The g-C being made up of step (2)3N4Powder, mixing and stirring, reactor is placed in baking oven at 150 DEG C heating 12h, treats
When naturally cooling to room temperature, obtained tan precipitate is carried out sucking filtration, through deionized water wash, in air dry oven 80 DEG C
Under be dried 4h after, be ground to powder, i.e. prepare a kind of visible light-responded g-C3N4/SnS2Composite photo-catalyst.
Further improvement of these options, in described step (1) and step (3), described SnCl4.5H2O and C2H5NS
Consumption mol ratio is 1: 2.
Further improvement of these options, in step (1) and step (3), described SnCl4.5H2The consumption of O is
5mmol, C2H5The consumption 10mmol of NS, the volume of described citric acid solution is 80ml, adds C2H5After NS, mixing time is specially
5min, CO (NH in step (2)2)2Consumption is 4g.
Further improvement of these options, in described step (3), described g-C3N4Consumption be that step (1) generates
SnS2The 25%-100% of quality.
Further improvement of these options, in described step (3), described g-C3N4Consumption be that step (1) generates
SnS2The 66.7% of quality.
The beneficial effects of the present invention is:
(1) method that the present invention uses solution blending, prepares g-C3N4And g-C3N4/SnS2Composite photo-catalyst, prepares work
Skill is simple, and material source enriches so that preparation cost reduces, and easily realizes large-scale production.
(2) present invention prepares g-C3N4/SnS2Composite photo-catalyst improves g-C3N4With SnS2Photoproduction current-carrying in nanoparticle
The separation efficiency of son, increases the life-span of photogenerated charge, promotes its photocatalytic activity.
(3) present invention prepares g-C3N4/SnS2Composite photo-catalyst not only inhibit electronics (e-)-hole (h+) to answer
Close, but also further increase the percent reduction to chromate waste water, it is often more important that can valency in substituted metal semi-conducting material
The metallic element that lattice are expensive, reduces cost and has good stability.
Accompanying drawing explanation
Fig. 1 is the visible light-responded g-C of one of the embodiment of the present invention 1 preparation3N4/SnS2The transmission electricity of composite photo-catalyst
Mirror figure.
Fig. 2 is the visible light-responded g-C of one of the embodiment of the present invention 2 preparation3N4/SnS2The transmission electricity of composite photo-catalyst
Mirror figure.
Fig. 3 is the visible light-responded g-C of one of the embodiment of the present invention 3 preparation3N4/SnS2The transmission electricity of composite photo-catalyst
Mirror figure.
Fig. 4 is the visible light-responded g-C of one of the embodiment of the present invention 4 preparation3N4/SnS2The transmission electricity of composite photo-catalyst
Mirror figure.
Fig. 5 is the SnS of comparative example 1 preparation2Transmission electron microscope picture.
Fig. 6 is the g-C of comparative example 2 preparation3N4Transmission electron microscope picture.
Fig. 7 is the SnS of comparative example 1 preparation2, comparative example 2 preparation g-C3N4And the g-C of embodiment 3 preparation3N4/SnS2
The full spectrogram of XPS of composite photo-catalyst.
Fig. 8 is the g-C of comparative example 2 preparation3N4And the g-C of embodiment 3 preparation3N4/SnS2The XPS's of composite photo-catalyst
C 1s schemes.
Fig. 9 is the SnS of comparative example 1 preparation2, comparative example 2 preparation g-C3N4And the g-C of embodiment 1～4 preparation3N4/
SnS2Composite photo-catalyst is with the expression activitiy figure of Cr (VI) in photo catalytic reduction water.
Detailed description of the invention
For the technological means making the present invention realize, creation characteristic, reach purpose and be easy to understand with effect, below in conjunction with
Detailed description of the invention, is expanded on further the present invention.
Embodiment 1
A kind of visible light-responded g-C3N4/SnS2The preparation method of composite photo-catalyst, its preparation process is as follows:
(1) Hydrothermal Synthesis SnS2: weigh the SnCl of 5mmol4.5H2O is put in reactor, adds 80mL 0.25mol/L's
Citric acid solution, adds the C of 10mmol after stirring and dissolving2H5NS, after continuing stirring 5min, is placed in reactor in baking oven 150
12h is heated at DEG C；When system naturally cools to room temperature, obtained tan precipitate is carried out sucking filtration, wash through deionization
Wash, after being dried 4h at 80 DEG C in air dry oven, be ground to powder and weigh；
(2) thermal polymerization legal system g-C3N4: weigh 4.0g CO (NH2)2Put in crucible, described crucible is being put into Muffle furnace
In, after being warming up to 540 DEG C with the speed of 20 DEG C/min, persistently calcine 2h, during after naturally cool to room temperature, by obtained light yellow
Product carries out sucking filtration, through deionized water wash, after being dried 4h at 80 DEG C in air dry oven, is ground to powder and preserves standby
With；
(3) Vacuum-assisted method g-C3N4/SnS2: weigh the SnCl of 5mmol4.5H2O is put in reactor, adds 80mL
The citric acid solution of 0.25mol/L, adds the C of 10mmol after stirring and dissolving2H5NS, after continuing stirring 5min, it is upper for adding quality
State the SnS that step (1) generates2The g-C being made up of step (2) of the 25% of quality3N4Powder, mixing and stirring, by reactor
It is placed in baking oven at 150 DEG C heating 12h, in time naturally cooling to room temperature, obtained tan precipitate is carried out sucking filtration, through going
Ionized water washs, and after being dried 4h, is ground to powder in air dry oven at 80 DEG C.
In order to observe the pattern after Material cladding, the product using transmission electron microscope to prepare the present embodiment characterizes, attached
Fig. 1 is the visible light-responded g-C of one prepared by the present embodiment3N4/SnS2The transmission electron microscope picture of composite photo-catalyst, A represents this reality
Execute g-C prepared by example3N4/SnS2Composite photo-catalyst.
Embodiment 2
A kind of visible light-responded g-C3N4/SnS2The preparation method of composite photo-catalyst, its preparation process is as follows:
(1) Hydrothermal Synthesis SnS2: weigh the SnCl of 5mmol4.5H2O is put in reactor, adds 80mL 0.25mol/L's
Citric acid solution, adds the C of 10mmol after stirring and dissolving2H5NS, after continuing stirring 5min, is placed in reactor in baking oven 150
12h is heated at DEG C；When system naturally cools to room temperature, obtained tan precipitate is carried out sucking filtration, wash through deionization
Wash, after being dried 4h at 80 DEG C in air dry oven, be ground to powder and weigh；
(2) thermal polymerization prepares g-C3N4: weigh 4.0g CO (NH2)2Put in crucible, described crucible is being put into Muffle
In stove, after being warming up to 540 DEG C with the speed of 20 DEG C/min, persistently calcine 2h, during after naturally cool to room temperature, by obtained pale yellow
Color product carries out sucking filtration, through deionized water wash, after being dried 4h at 80 DEG C in air dry oven, is ground to powder and preserves standby
With；
(3) Vacuum-assisted method g-C3N4/SnS2: weigh the SnCl of 5mmol4.5H2O is put in reactor, adds 80mL
The citric acid solution of 0.25mol/L, adds the C of 10mmol after stirring and dissolving2H5NS, after continuing stirring 5min, it is upper for adding quality
State the SnS that step (1) generates2The g-C being made up of step (2) of the 42.8% of quality3N4Powder, mixing and stirring, will reaction
Still is placed in baking oven at 150 DEG C heating 12h, in time naturally cooling to room temperature, obtained tan precipitate is carried out sucking filtration, warp
Deionized water wash, after being dried 4h, is ground to powder in air dry oven at 80 DEG C.
In order to observe the pattern after Material cladding, the product using transmission electron microscope to prepare the present embodiment characterizes, attached
Fig. 2 is the visible light-responded g-C of one prepared by the present embodiment3N4/SnS2The transmission electron microscope picture of composite photo-catalyst, B represents this reality
Execute g-C prepared by example3N4/SnS2Composite photo-catalyst.
Embodiment 3
A kind of visible light-responded g-C3N4/SnS2The preparation method of composite photo-catalyst, its preparation process is as follows:
(1) Hydrothermal Synthesis SnS2: weigh the SnCl of 5mmol4.5H2O is put in reactor, adds 80mL 0.25mol/L's
Citric acid solution, adds the C of 10mmol after stirring and dissolving2H5NS, after continuing stirring 5min, is placed in reactor in baking oven 150
12h is heated at DEG C；When system naturally cools to room temperature, obtained tan precipitate is carried out sucking filtration, wash through deionization
Wash, after being dried 4h at 80 DEG C in air dry oven, be ground to powder and weigh；
(2) thermal polymerization prepares g-C3N4: weigh 4.0g CO (NH2)2Put in crucible, described crucible is being put into Muffle
In stove, after being warming up to 540 DEG C with the speed of 20 DEG C/min, persistently calcine 2h, during after naturally cool to room temperature, by obtained pale yellow
Color product carries out sucking filtration, through deionized water wash, after being dried 4h at 80 DEG C in air dry oven, is ground to powder and preserves standby
With；
(3) Vacuum-assisted method g-C3N4/SnS2: weigh the SnCl of 5mmol4.5H2O is put in reactor, adds 80mL
The citric acid solution of 0.25mol/L, adds the C of 10mmol after stirring and dissolving2H5NS, after continuing stirring 5min, it is upper for adding quality
State the SnS that step (1) generates2The g-C being made up of step (2) of the 66.7% of quality3N4Powder, mixing and stirring, will reaction
Still is placed in baking oven at 150 DEG C heating 12h, in time naturally cooling to room temperature, obtained tan precipitate is carried out sucking filtration, warp
Deionized water wash, after being dried 4h, is ground to powder in air dry oven at 80 DEG C.
In order to observe the pattern after Material cladding, the product using transmission electron microscope to prepare the present embodiment characterizes, attached
Fig. 3 is the visible light-responded g-C of one prepared by the present embodiment3N4/SnS2The transmission electron microscope picture of composite photo-catalyst, C represents this reality
Execute g-C prepared by example3N4/SnS2Composite photo-catalyst.
Embodiment 4
A kind of visible light-responded g-C3N4/SnS2The preparation method of composite photo-catalyst, its preparation process is as follows:
(1) Hydrothermal Synthesis SnS2: weigh the SnCl of 5mmol4.5H2O is put in reactor, adds 80mL 0.25mol/L's
Citric acid solution, adds the C of 10mmol after stirring and dissolving2H5NS, after continuing stirring 5min, is placed in reactor in baking oven 150
12h is heated at DEG C；When system naturally cools to room temperature, obtained tan precipitate is carried out sucking filtration, wash through deionization
Wash, after being dried 4h at 80 DEG C in air dry oven, be ground to powder and weigh；
(2) thermal polymerization prepares g-C3N4: weigh 4.0g CO (NH2)2Put in crucible, described crucible is being put into Muffle
In stove, after being warming up to 540 DEG C with the speed of 20 DEG C/min, persistently calcine 2h, during after naturally cool to room temperature, by obtained pale yellow
Color product carries out sucking filtration, through deionized water wash, after being dried 4h at 80 DEG C in air dry oven, is ground to powder and preserves standby
With；
(3) Vacuum-assisted method g-C3N4/SnS2: weigh the SnCl of 5mmol4.5H2O is put in reactor, adds 80mL
The citric acid solution of 0.25mol/L, adds the C of 10mmol after stirring and dissolving2H5NS, continue stirring 5min after, add quality be with
The SnS that above-mentioned steps (1) generates2The g-C being made up of step (2) of the 100% of quality3N4Powder, mixing and stirring, will be anti-
Answer still to be placed in baking oven at 150 DEG C heating 12h, in time naturally cooling to room temperature, obtained tan precipitate carried out sucking filtration,
Through deionized water wash, after being dried 4h at 80 DEG C in air dry oven, it is ground to powder.
In order to observe the pattern after Material cladding, the product using transmission electron microscope to prepare the present embodiment characterizes, attached
Fig. 4 is the visible light-responded g-C of one prepared by the present embodiment3N4/SnS2The transmission electron microscope picture of composite photo-catalyst, D represents this reality
Execute g-C prepared by example3N4/SnS2Composite photo-catalyst.
Comparative example 1
Hydrothermal Synthesis SnS2
Weigh 5mmolSnCl4.5H2O puts into reactor, adds the citric acid solution of 80mL 0.25mol/L, stirring and dissolving
The C of rear addition 10mmol2H5NS, after continuing stirring 5min, is placed in reactor in baking oven at 150 DEG C heating 12h, treats system
When naturally cooling to room temperature, obtained tan precipitate is carried out sucking filtration, through deionized water wash, in air dry oven 80
After being dried 4h at DEG C, it is ground to powder and saves backup.
In order to observe the pattern after Material cladding, the product using transmission electron microscope to prepare the present embodiment characterizes, attached
Fig. 5 is a kind of SnS prepared by this comparative example2Transmission electron microscope picture.
Comparative example 2
Thermal polymerization legal system g-C3N4
Weigh 4.0gCO (NH2)2Put in crucible, described crucible is being put in Muffle furnace, with the speed liter of 20 DEG C/min
After warm to 540 DEG C, persistently calcine 2h, during after naturally cool to room temperature, obtained light yellow product is carried out sucking filtration, through deionization
Water washs, and after being dried 4h, is ground to powder and saves backup in air dry oven at 80 DEG C；
In order to observe the pattern after Material cladding, the product using transmission electron microscope to prepare this comparative example characterizes, attached
Fig. 6 is a kind of g-C prepared by this comparative example3N4Transmission electron microscope picture.
Based on above-mentioned, from accompanying drawing 5, can be seen that SnS2Present relatively regular hexagonal nano lamellar.G-after hydrothermal treatment consists
C3N4Changing the block accumulation after thermal polymerization, accompanying drawing 6 presents the most random lamellar structure.This is because hydro-thermal reaction
Temperature high and the time is long, the relatively g-C of chunk shape3N4Gradually peel off flakiness shape.Observe composite A～the picture of D, permissible
Find out the SnS of hexagonal flake2It is gathered in thin layer g-C in a large number3N4On, and contact closely；From the picture comparative analysis of A～C along with
g-C3N4The increase of consumption, the two tightness degree combined increases, and forms close heterojunction structure.At g-C3N4Content is maximum
D figure in find out in addition to the two combine closely, the most barish g-C3N4.The heterojunction structure of composite have impact on
Photocatalysis effect.
Fig. 7 gives SnS2、g-C3N4/SnS2And g-C3N4XPS figure.From g-C3N4/SnS2XPS figure can be seen that sample
Containing tetra-kinds of elements of Sn, S, C and N in product.SnS2And g-C3N4/SnS2Sn 3d5/2With S 2p3/2Combination can all exist
486.7eV and 161.7eV.From g-C3N4/SnS2And g-C3N4XPS full spectrogram spectrum in can be seen that both N 1s combine and can distinguish
It is 399.67eV and 398.8eV, there occurs that some offset.
G-C shown in Fig. 83N4And g-C3N4/SnS2The combination at C 1s peak can be 284.6,288.2 and 284.8 and
288.5eV, the peak of the corresponding carbon impurity (carbon dioxide in air) introduced and 288.2eV is attributed to C-N-C combination respectively
Carbon.By above analyze show tetra-kinds of elements of Sn, S, C and N combination can respectively with SnS2And g-C3N4In corresponding, table
Its bond styles bright does not changes, but the combination of C 1s and N 1s can offset, and may be formed during compound
Heterojunction structure causes, and further illustrates the g-C in synthesis3N4/SnS2Middle g-C3N4And SnS2Structure is not destroyed, both
There occurs effective compound.
Accompanying drawing 9 is that xenon lamp (λ > 420nm) irradiates lower 300mg SnS2, embodiment 1～4 preparation g-C3N4/SnS2Complex light
Catalyst and g-C3N4Photo catalytic reduction is with 50mg/LK2Cr2O7Aqueous solution is the expression activitiy of Cr (VI) in pollutant model.From
Figure can be seen that first, with SnS2, embodiment 1～4 preparation g-C3N4/SnS2Composite photo-catalyst and g-C3N4At xenon lamp
When carrying out Cr (VI) in photo catalytic reduction water under irradiation, the product of all synthesis all has light-catalysed ability, and embodiment 1
～4 preparation g-C3N4/SnS2The photocatalytic activity of composite photo-catalyst is intended to compare SnS2And g-C3N4One-component higher, say
Bright g-C3N4/SnS2Composite can improve SnS further2Photocatalytic activity.3rd, there is different g-C3N4Answering of content
The g-C of condensation material embodiment 1～4 preparation3N4/SnS2The photocatalytic activity of composite photo-catalyst has bigger difference, its photocatalysis
Order is C > D > B > A, and in the case of same light application time, the photocatalytic activity of joint product is along with g-C3N4Quality hundred
The increase of content is divided to be gradually increased, along with g-C3N4The continuation of weight/mass percentage composition when increasing, the photocatalysis of joint product is lived
Property begins to decline again.The most described g-C3N4Consumption be the SnS that step (1) generates2Quality 66.7% time, g-C3N4/SnS2
There is optimal photocatalysis effect.
Those of ordinary skill in the art it should be appreciated that above embodiment be intended merely to illustrate the present invention,
And be not used as limitation of the invention, the change as long as in the spirit of the present invention, to embodiment described above
Change, modification all will fall in scope of the presently claimed invention.
Claims (5)
1. a visible light-responded g-C3N4/SnS2The preparation method of composite photo-catalyst, it is characterised in that: its preparation process is such as
Under:
(1) Hydrothermal Synthesis SnS2: take a certain amount of SnCl4.5H2O is put in reactor, adds the citric acid solution of 0.25mol/L,
A certain amount of C is added after stirring and dissolving2H5NS, after continuing stirring a period of time, is placed in reactor in baking oven and adds at 150 DEG C
Hot 12h, when system naturally cools to room temperature, carries out sucking filtration by obtained tan precipitate, through deionized water wash, is rousing
After wind drying baker is dried 4h at 80 DEG C, it is ground to powder and weighs；
(2) thermal polymerization prepares g-C3N4: take a certain amount of CO (NH2)2Put in crucible, described crucible is being put into Muffle furnace
In, after being warming up to 540 DEG C with the speed of 20 DEG C/min, persistently calcine 2h, during after naturally cool to room temperature, by obtained light yellow
Product carries out sucking filtration, through deionized water wash, after being dried 4h at 80 DEG C in air dry oven, is ground to powder and preserves standby
With；
(3) Vacuum-assisted method g-C3N4/SnS2: weigh a certain amount of SnCl4.5H2O is put in reactor, adds 0.25mol/L lemon
Lemon acid solution, adds a certain amount of C after stirring and dissolving2H5NS, after continuing stirring a period of time, weighs a certain amount of by step (2)
The g-C made3N4Powder, mixing and stirring, reactor is placed in baking oven at 150 DEG C heating 12h, waits to naturally cool to
During room temperature, obtained tan precipitate is carried out sucking filtration, through deionized water wash, air dry oven is dried at 80 DEG C 4h
After, it is ground to powder, i.e. prepares a kind of visible light-responded g-C3N4/SnS2Composite photo-catalyst.
The visible light-responded g-C of one the most according to claim 13N4/SnS2The preparation method of composite photo-catalyst, it is special
Levy and be: in described step (1) and step (3), described SnCl4.5H2O and C2H5NS consumption mol ratio is 1: 2.
The visible light-responded g-C of one the most according to claim 23N4/SnS2The preparation method of composite photo-catalyst, it is special
Levy and be: in step (1) and step (3), described SnCl4.5H2The consumption of O is 5mmol, C2H5The consumption 10mmol of NS, institute
The volume stating citric acid solution is 80ml, adds C2H5After NS, mixing time is specially 5min；CO (NH in step (2)2)2Consumption
For 4g.
The visible light-responded g-C of one the most according to claim 23N4/SnS2The preparation method of composite photo-catalyst, it is special
Levy and be: in described step (3), described g-C3N4Consumption be the SnS that step (1) generates2The 25%-100% of quality.
The visible light-responded g-C of one the most according to claim 43N4/SnS2The preparation method of composite photo-catalyst, it is special
Levy and be: in described step (3), described g-C3N4Consumption be the SnS that step (1) generates2The 66.7% of quality.
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