CN108816248A - Application of the copper and indium zinc sulphur/redox graphene nanocomposite in photocatalysis removal oxynitrides - Google Patents
Application of the copper and indium zinc sulphur/redox graphene nanocomposite in photocatalysis removal oxynitrides Download PDFInfo
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- CN108816248A CN108816248A CN201810689382.1A CN201810689382A CN108816248A CN 108816248 A CN108816248 A CN 108816248A CN 201810689382 A CN201810689382 A CN 201810689382A CN 108816248 A CN108816248 A CN 108816248A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000010949 copper Substances 0.000 title claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 24
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000007790 solid phase Substances 0.000 claims description 14
- 239000006194 liquid suspension Substances 0.000 claims description 12
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- 235000011150 stannous chloride Nutrition 0.000 claims description 10
- 239000001119 stannous chloride Substances 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 150000002471 indium Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical class Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 230000001413 cellular effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 54
- 239000012071 phase Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000003321 amplification Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 graphene compound Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000505 pernicious effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical class [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- 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
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- Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
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Abstract
The present invention relates to application of the copper and indium zinc sulphur/redox graphene nanocomposite in photocatalysis removal oxynitrides, belong to semiconductor nano material technical field, wherein CIZS nanostructure is as I-III-VI2The alloy compound semiconductor of race and II-VI group has suitable band gap, and special electronic band structure, band gap is adjustable, good chemistry and thermal stability.Meanwhile rGO can efficiently separate electron-hole pair, and by adjusting the mass fraction of rGO in the composite material, to reach the band gap and specific surface area that adjust the composite material, and then improve the composite material and act on the photocatalysis removal of oxynitrides.Because rGO has bi-dimensional cellular shape structure, specific surface area can be increased, so that reactant is had bigger reaction site, and then improve photocatalytic activity.
Description
Technical field
The invention belongs to semiconductor nano material technical fields, and in particular to copper and indium zinc sulphur/redox graphene nanometer
Application of the composite material in photocatalysis removal oxynitrides.
Background technique
In today that environmental pollution is getting worse, the environmental problem that organic pollutant and pernicious gas cause is caused
More and more concerns, wherein atmosphere pollution nitric oxide (NO) causes the formation of acid rain and photochemical fog at branch, sternly
Environment is destroyed again and endangers human health.Currently, photocatalysis technology is since its reaction condition is not violent, energy consumption is lower, product
The advantages that secondary pollution, high catalytic efficiency will not be caused to environment, it is considered to be one kind of removal nitric oxide (NO) most has latent
The environmentally friendly technology of power.But common light-catalyst ZnO, TiO2, CdS etc. all have the defects that it is more or less, such as
Reactivity is low, low to the utilization rate of sunlight, containing the big heavy metal etc. of toxicity.So people are badly in need of finding one kind efficiently just
Prompt nontoxic method controls and removes the pernicious gases such as the nitric oxide (NO) in air.
Summary of the invention
In view of this, one of the objects of the present invention is to provide copper and indium zinc sulphur/redox graphene nanocomposites
Application in photocatalysis removal oxynitrides.The present invention is subsidized by national defence section work office project, Funded Projects number：
JCKY2017110C065。
In order to achieve the above objectives, the present invention provides the following technical solutions：
1, application of the copper and indium zinc sulphur/redox graphene nanocomposite in photocatalysis removal oxynitrides.
Further, in the copper and indium zinc sulphur/redox graphene nanocomposite redox graphene quality
Score is 10-40%.
Further, in the copper and indium zinc sulphur/redox graphene nanocomposite redox graphene quality
Score is 30%.
Further, the oxynitrides is NO or NO2One of or it is a variety of.
Further, the preparation method of the copper and indium zinc sulphur/redox graphene nanocomposite is as follows：
(1) in mass ratio 438:131.8:1.89:400 is soluble in water together by zinc salt, indium salts, mantoquita and sulfosalt, stirring
It is 1.89 by the mass ratio of mantoquita and redox graphene after mixing:6.8-27.2 redox graphene is added, ultrasound
Forerunner's liquid suspension is obtained after 20-30min；
(2) the forerunner's liquid suspension obtained in step (1) is transferred in reaction kettle and is sealed, reacted at 160-200 DEG C
It is separated by solid-liquid separation to obtain solid phase after 16-18h, copper and indium zinc sulphur/redox graphene is made after the solid phase is cleaned, dry and receives
Nano composite material.
Further, in step (1), the zinc salt is zinc acetate, and the indium salts are in indium acetate or four water indium trichlorides
One kind, the mantoquita are stannous chloride, and the sulfosalt is thioacetamide.
Further, described to be separated by solid-liquid separation as to be taken after the speed of 6000-9000r/min centrifugation 5-10min in step (2)
Lower layer's solid phase.
Further, in step (2), the cleaning is first with water eccentric cleaning 3-5 times, then with dehydrated alcohol eccentric cleaning 3-
5 times.
Further, in step (2), the drying dry 6-10h at 50-70 DEG C.
The beneficial effects of the present invention are：The present invention provides copper and indium zinc sulphur/redox graphene nanocomposites
The application of (CIZS/rGO composite material) in photocatalysis removal oxynitrides.Wherein, CIZS nanostructure is as I-III-
VI2The alloy compound semiconductor of race and II-VI group has suitable band gap, and special electronic band structure, band gap is adjustable, good
Good chemistry and thermal stability.Meanwhile rGO can efficiently separate electron-hole pair, and by adjusting in the composite material
The mass fraction of rGO to reach the band gap and specific surface area that adjust the composite material, and then improves the composite material to nitrogen
The photocatalysis removal of oxygen compound acts on.Because compound can be improved to the absorptivity of visible light in suitable band gap, such as
TiO2Band gap be that~2.7eV so it only has (~5%) to the utilization rate of visible light cannot effectively utilize sunlight,
So suitable band gap can be improved to can be by the absorption efficiency of light.In addition, rGO bi-dimensional cellular shape structure, can increase and compare table
Area makes reactant have bigger reaction site, further improves photocatalytic activity.
Copper and indium zinc sulphur/redox graphene nanocomposite (CIZS/rGO composite material) photocatalysis is gone in the present invention
Except the principle of oxynitrides is as follows：
CIZS/rGO+visible light→h+ VB+e- CB (1)
Under visible light illumination, electronics can be energized into conduction band (CB) from valence band (VB), leave sky in the valence band of CIZS
Cave (process (1)).These holes are reacted with the OH- of adsorption and water generates OH free radical to carry out NO oxidation (process
(2))
H2O+h+ VB→·OH+H+ (2)
h+ VB+NO→NOχ (3)
Due to higher than the half-cell reduction potential of standard at the top of the valence band of CIZS, so the hole in valence band can also be straight
Connect oxidation NO (process (3)).There are two destiny for excitation electronics on the conduction band of CIZS：With O2Reaction generates superoxides (process
(4)), hydrogen peroxide (process (5)) and OH free radical (process (6)), and reconfigured with the hole in valence band.
e- CB+O2→·O2 - (4)
·O2 -+2H++e- CB→H2O2 (5)
H2O2+e- CB→·OH+OH- (6)
The strong chemical bond of CIZS and rGO will lead to transmission of the light induced electron from the conduction band of CIZS to rGO.At the same time, such as
Preceding described, the Schottky barrier formed on the interface CIZS/rGO can prevent the reversed of conduction band of the photoelectron from rGO to CIZS
It transports.To inhibit the compound of the surface CIZS photoelectron and hole, these more effectively separate electrons and holes and can produce
More living radical (OH and O2- etc.) oxidations NO (process (7)-(10)).
NO+2·OH→NO2+H2O (7)
NO2+·OH→NO3 -+H (8)
NO+NO2+H2O→2HNO2 (9)
NOχ+·O2 -→NO3 (10)
Detailed description of the invention
In order to keep the purpose of the present invention, technical scheme and beneficial effects clearer, the present invention provides following attached drawing and carries out
Explanation：
Fig. 1 is pure redox graphene, the pure phase copper and indium zinc sulfur materials prepared in comparative example and makes in embodiment 3
Standby copper and indium zinc sulphur/redox graphene nanocomposite scanning electron microscope (SEM) photograph；(a is pure to prepare in comparative example
The scanning electron microscope (SEM) photograph of phase copper and indium zinc sulphur amplifies 80000 times；B is the scanning electron microscope (SEM) photograph of pure redox graphene, amplification 20000
Times；C and d is the copper and indium zinc sulphur/redox graphene nanocomposite scanning electron microscope (SEM) photograph prepared in embodiment 3, point
It Fang great not be 20000 times and 80000 times)
Fig. 2 is constituent content figure in the copper and indium zinc sulphur/redox graphene nanocomposite prepared in embodiment 3；
Fig. 3 is distribution diagram of element in the copper and indium zinc sulphur/redox graphene nanocomposite prepared in embodiment 3；
Fig. 4 is the pure phase copper and indium zinc sulfur materials prepared in comparative example and embodiment 1, embodiment 2, embodiment 3 and reality
Apply the copper and indium zinc sulphur/redox graphene nanocomposite UV-vis absorption spectrum figure prepared in example 4；
Fig. 5 is the pure phase copper and indium zinc sulfur materials prepared in comparative example and embodiment 1, embodiment 2, embodiment 3 and reality
The copper and indium zinc sulphur/redox graphene nanocomposite prepared in example 4 is applied under visible light to the photocatalysis removal effect of NO
Rate figure.
Specific embodiment
Below by a preferred embodiment of the present invention will be described in detail.
Embodiment 1
It prepares copper and indium zinc sulphur/redox graphene nanocomposite (CIZS/rGO composite material)
(1) in mass ratio 438:131.8:1.89:400 by zinc acetate, indium acetate, stannous chloride and thioacetamide together
It is dissolved in deionized water, is 1.89 by the mass ratio of stannous chloride and redox graphene after stirring 30min:6.8 being added
Redox graphene obtains forerunner's liquid suspension after ultrasonic 20min；
(2) the forerunner's liquid suspension obtained in step (1) is transferred in reaction kettle and is sealed, after reacting 16h at 200 DEG C
It is centrifuged 5min Hou Qu lower layer solid phase with the speed of 9000r/min, by the solid phase first with deionized water eccentric cleaning 3 times, then with nothing
6h is dried after water-ethanol eccentric cleaning 3 times at 70 DEG C, copper and indium zinc sulphur/redox graphene nanocomposite is made,
The mass fraction of redox graphene is 10% in middle copper and indium zinc sulphur/redox graphene nanocomposite.
Embodiment 2
It prepares copper and indium zinc sulphur/redox graphene nanocomposite (CIZS/rGO composite material)
(1) in mass ratio 438:131.8:1.89:400 by zinc acetate, indium acetate, stannous chloride and thioacetamide together
It is dissolved in deionized water, is 1.89 by the mass ratio of stannous chloride and redox graphene after stirring 30min:13.6 are added
Redox graphene obtains forerunner's liquid suspension after ultrasonic 25min；
(2) the forerunner's liquid suspension obtained in step (1) is transferred in reaction kettle and is sealed, after reacting 18h at 160 DEG C
It is centrifuged 10min Hou Qu lower layer solid phase with the speed of 6000r/min, by the solid phase first with deionized water eccentric cleaning 5 times, then with
10h is dried after dehydrated alcohol eccentric cleaning 5 times at 50 DEG C, copper and indium zinc sulphur/redox graphene nanocomposite is made,
Wherein the mass fraction of redox graphene is 20% in copper and indium zinc sulphur/redox graphene nanocomposite.
Embodiment 3
It prepares copper and indium zinc sulphur/redox graphene nanocomposite (CIZS/rGO composite material)
(1) in mass ratio 438:131.8:1.89:400 by zinc acetate, indium acetate, stannous chloride and thioacetamide together
It is dissolved in deionized water, is 1.89 by the mass ratio of stannous chloride and redox graphene after stirring 30min:20.4 are added
Redox graphene obtains forerunner's liquid suspension after ultrasonic 30min；
(2) the forerunner's liquid suspension obtained in step (1) is transferred in reaction kettle and is sealed, after reacting 18h at 180 DEG C
It is centrifuged 6min Hou Qu lower layer solid phase with the speed of 8000r/min, by the solid phase first with deionized water eccentric cleaning 4 times, then with nothing
10h is dried after water-ethanol eccentric cleaning 4 times at 60 DEG C, copper and indium zinc sulphur/redox graphene nanocomposite is made,
The mass fraction of redox graphene is 30% in middle copper and indium zinc sulphur/redox graphene nanocomposite.
Embodiment 4
It prepares copper and indium zinc sulphur/redox graphene nanocomposite (CIZS/rGO composite material)
(1) in mass ratio 438:131.8:1.89:400 by zinc acetate, indium acetate, stannous chloride and thioacetamide together
It is dissolved in deionized water, is 1.89 by the mass ratio of stannous chloride and redox graphene after stirring 30min:27.2 are added
Redox graphene obtains forerunner's liquid suspension after ultrasonic 25min；
(2) the forerunner's liquid suspension obtained in step (1) is transferred in reaction kettle and is sealed, after reacting 17h at 185 DEG C
It is centrifuged 8min Hou Qu lower layer solid phase with the speed of 7000r/min, by the solid phase first with deionized water eccentric cleaning 3 times, then with nothing
8h is dried after water-ethanol eccentric cleaning 3 times at 65 DEG C, copper and indium zinc sulphur/redox graphene nanocomposite is made,
The mass fraction of redox graphene is 40% in middle copper and indium zinc sulphur/redox graphene nanocomposite.
Comparative example
The difference from embodiment 1 is that being added without redox graphene during the preparation process, pure phase copper and indium is finally made
Zinc sulfur materials (CIZS material).
Using surface sweeping Electronic Speculum respectively to the pure phase copper and indium zinc sulfur materials prepared in pure redox graphene, comparative example
Be scanned with the copper and indium zinc sulphur/redox graphene nanocomposite prepared in embodiment 3, as a result as shown in Figure 1,
A is the scanning electron microscope (SEM) photograph of the pure phase copper and indium zinc sulphur prepared in comparative example in Fig. 1, and amplification factor is 80000 times, b in Fig. 1
For the scanning electron microscope (SEM) photograph of pure redox graphene, amplification factor is 20000 times, and c and d is to prepare in embodiment 3 in Fig. 1
Copper and indium zinc sulphur/redox graphene nanocomposite scanning electron microscope (SEM) photograph, amplification factor be respectively 20000 times and
80000 times, as shown in Figure 1, copper and indium zinc sulfur materials are in nanosphere shape, and are attached to redox graphene surface, are formed different
Matter knot.
The content of each element in the copper and indium zinc sulphur/redox graphene nanocomposite prepared in analysis embodiment 3,
As a result as shown in Figure 2 and Table 1, by Fig. 2 and table 1 it is found that only existing six kinds of elements in the material, be respectively C, O, Cu, In,
Zn, S, and other elements are not present, mass ratio shared by each element is respectively 8.51%, 2.14%, 0.7%, 26.52%,
30.63%, 31.52%.
The content of each element in the copper and indium zinc sulphur/redox graphene nanocomposite prepared in 1 embodiment 3 of table
| Element | Mass percent | Atomic percent |
| Cu | 0.7% | 0.43% |
| In | 26.52% | 9.11% |
| Zn | 30.63% | 18.48% |
| S | 31.52% | 38.77% |
| C | 8.51% | 27.94% |
| O | 2.14% | 5.27% |
The distribution of each element in the copper and indium zinc sulphur/redox graphene nanocomposite prepared in analysis embodiment 3
Situation illustrates that redox graphene equably divides as a result as shown in figure 3, from the figure 3, it may be seen that six kinds of elements are all uniformly distributed
Cloth forms close heterojunction structure in copper and indium zinc sulfur materials surface, the two.Heterojunction structure is formed such that photoinduction in copper and indium zinc
The electronics that sulfur materials surface generates can be soon transferred on redox graphene, reduced the distance of charge transmission, added
Fast electronics-hole pair rate of departure, facilitates photocatalysis and removes active raising.
Using ultraviolet spectrometer respectively to prepared in comparative example pure phase copper and indium zinc sulfur materials and embodiment 1, implement
The copper and indium zinc sulphur/redox graphene nanocomposite prepared in example 2, embodiment 3 and embodiment 4 is analyzed, as a result
As shown in figure 4, as shown in Figure 4, with redox graphene in copper and indium zinc sulphur/redox graphene nanocomposite
The increase of amount, it is seen that the absorption of light gradually increases, and red shift occurs for copper and indium zinc sulphur/redox graphene compound ABSORPTION EDGE.
Meanwhile the variation of each sample color also demonstrates this point because it was found that, pure phase copper and indium zinc sulfur materials present yellow,
After redox graphene is added, nanocomposite becomes olive colour, with the increase of redox graphene amount, face
Also darkness deepens for color.
Embodiment 5
Application of the copper and indium zinc sulphur/redox graphene nanocomposite in photocatalysis removal oxynitrides
The copper and indium zinc sulphur/redox graphene nanocomposite prepared in testing example 1-4 respectively at room temperature
With the copper and indium zinc sulfur materials that prepare in comparative example to the removal ability of NO, the example reaction room in test is that volume is
4.5L, length 30cm, width 15cm are highly the rectangular reactor of 10cm, which is made simultaneously of polymer glass
Organic glass is covered, and is sealed with quartz glass lid.The 150W for the UV edge filter (420nm) for being used to irradiate is commercial
Tungsten halogen lamp (General Electric Co. Limited) is vertically disposed in right above reactor.The step of specific test, is as follows：
(1) sample preparation
The sample powder for weighing 200mg first is fully ground, and then averagely pours into the powder after grinding in two test tubes,
Each each 100mg powder of test tube, then then will respectively to the ethyl alcohol dispersion and ultrasound 20min that 15mL is respectively added in two test tubes
The mixed solution of two test tubes is poured into respectively in the identical glass dish of two sizes (diameter 12cm), is placed in 60 DEG C of environment and is dried
Dry 7h.
(2) distribution
NO gas in test is the compressed gas cylinder of 100ppm (N2 balance) from concentration.The initial concentration of NO is diluted
To about 600ppb.The flow of air stream and NO are respectively maintained at 2.4L/min and 15mL/min.Then by two kinds of gases in threeway
It mixes in valve.The expectation relative humidity level that NO flows in air stream is maintained at 50%.When obtaining absorption/desorption balance,
Lamp is opened, by the outlet of rectangle sample reaction chamber and NOxAnalyzer is connected to together, interval time 1min, then to NO, NO2
And NOx(NO+NO2) concentration carries out sampling and test and obtain final test data.
(3) test record
By load there is the glass dish of sample catalyst to be placed in photo catalysis reactor, and using quartz glass lid come by its
Closing.Then NO is passed through in reactor, NO concentration is observed by analyzer, opens light source after balance to be achieved, it is continuous to survey
Determine 30min.Concentration delta data by analyzing NO can characterize its photocatalysis performance.Material is following formula to the removal rate of NO：
η (%)=(C0-C)/C0* 100%
Wherein, C0Indicate the equilibrium concentration that NO reaches in reactor before turning on light, C indicates the real-time concentration of NO after turning on light.
Experimental result is shown in Fig. 5, as shown in Figure 5, with restoring in copper and indium zinc sulphur/redox graphene nanocomposite
The increase of the amount of graphene oxide, the material first become larger to the photocatalysis of NO removal activity, after gradually become smaller, possible reason
It is that excessive redox graphene can block aperture in copper and indium zinc sulphur nanosphere, causes specific surface area to decline, while mistake
The redox graphene of amount restrains the separation of electron-hole, results in the reduction of photocatalysis efficiency.Wherein, when copper and indium zinc
When the mass fraction of redox graphene is 30% in sulphur/redox graphene nanocomposite, the photocatalysis to NO
Removal activity has reached 59.79%, improves 47% relative to pure phase copper and indium zinc sulfur materials.
Copper and indium zinc sulphur/redox graphene nanocomposite not only removes the photocatalysis that NO has had in the present invention
Effect equally also has good photocatalysis removal for the mixture of other oxynitrides or other oxynitrides
Effect.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (9)
1. application of the copper and indium zinc sulphur/redox graphene nanocomposite in photocatalysis removal oxynitrides.
2. application as described in claim 1, which is characterized in that the copper and indium zinc sulphur/nano combined material of redox graphene
The mass fraction of redox graphene is 10-40% in material.
3. application as claimed in claim 2, which is characterized in that the copper and indium zinc sulphur/nano combined material of redox graphene
The mass fraction of redox graphene is 30% in material.
4. application as described in claim 1, which is characterized in that the oxynitrides is NO or NO2One of or it is a variety of.
5. application as described in claim 1, which is characterized in that the copper and indium zinc sulphur/nano combined material of redox graphene
The preparation method of material is as follows：
(1) in mass ratio 438:131.8:1.89:400 is soluble in water together by zinc salt, indium salts, mantoquita and sulfosalt, stirs and evenly mixs
It afterwards, is 1.89 by the mass ratio of mantoquita and redox graphene:Redox graphene, ultrasonic 20- is added in 6.8-27.2
Forerunner's liquid suspension is obtained after 30min；
(2) the forerunner's liquid suspension obtained in step (1) is transferred in reaction kettle and is sealed, react 16- at 160-200 DEG C
It is separated by solid-liquid separation to obtain solid phase after 18h, copper and indium zinc sulphur/redox graphene nanometer is made after the solid phase is cleaned, dry and answers
Condensation material.
6. application as claimed in claim 5, which is characterized in that in step (1), the zinc salt is zinc acetate, and the indium salts are
One of indium acetate or four water indium trichlorides, the mantoquita are stannous chloride, and the sulfosalt is thioacetamide.
7. application as claimed in claim 5, which is characterized in that described to be separated by solid-liquid separation as with 6000-9000r/ in step (2)
The speed of min is centrifuged 5-10min Hou Qu lower layer solid phase.
8. application as claimed in claim 5, which is characterized in that in step (2), the cleaning is first with water eccentric cleaning 3-5
It is secondary, then with dehydrated alcohol eccentric cleaning 3-5 times.
9. application as claimed in claim 5, which is characterized in that in step (2), the drying dry 6- at 50-70 DEG C
10h。
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