CN110075895A - A kind of carbon nitrence-zinc sulphide composite nano materials and its preparation method and application - Google Patents
A kind of carbon nitrence-zinc sulphide composite nano materials and its preparation method and application Download PDFInfo
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- CN110075895A CN110075895A CN201910274863.0A CN201910274863A CN110075895A CN 110075895 A CN110075895 A CN 110075895A CN 201910274863 A CN201910274863 A CN 201910274863A CN 110075895 A CN110075895 A CN 110075895A
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- zinc sulphide
- carbon nitrence
- nano materials
- composite nano
- nitrence
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011941 photocatalyst Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 15
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- -1 Ethyl alcohol Chemical compound 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- YYNIVGIURMZWQU-UHFFFAOYSA-N diethyl(hexadecyl)azanium;bromide Chemical group Br.CCCCCCCCCCCCCCCCN(CC)CC YYNIVGIURMZWQU-UHFFFAOYSA-N 0.000 claims description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 238000007592 spray painting technique Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013034 coating degradation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 229940035637 spectrum-4 Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- 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
- B01D53/007—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 by irradiation
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
Abstract
The invention discloses a kind of carbon nitrence-zinc sulphide composite nano materials and its preparation method and application, the granularity of the material is 30-100nm, and the content of carbon nitrence is 5-25wt%, and surplus is zinc sulphide.The method is that zinc source, g-C3N4 nanometer sheet, surfactant and sulphur source are added in first backward ethanol water, ultrasonic disperse, and separation, washing, drying after hydro-thermal reaction can obtain the composite nano materials.By the composite nano materials and curing agent and filler ball milling, inorganic bond is added, it stirs evenly, obtain spraying slurry, it is sprayed into substrate surface with 0.4~0.6m/s, 0.45~0.55MPa, after multistage heat treatment, cleans, dries, obtain the carbon nitrence/zinc sulphide composite photocatalyst coating.Preparation process of the present invention is simple, has stronger Degradation Formaldehyde ability with its composite photocatalyst coating prepared, can have important application in the fields such as air cleaning, sewage treatment.
Description
Technical field
The present invention relates to nano material and environment-friendly materials field, be related to a kind of carbon nitrence-zinc sulphide composite nano materials and
Preparation method and application.
Background technique
It is widely used in due to its excellent physical and chemical performance using titanium dioxide as traditional catalysis material of representative
Optical catalytic environment purification is one of the important channel of problem of environmental pollution for solving currently to be on the rise.Currently based on titanium dioxide
The core of the photocatalysis technology application of titanium is mainly to improve itself photocatalysis performance and plated film bond strength.However titanium dioxide
It is only capable of absorbing in solar spectrum 4%~5% ultraviolet light, it is seen that light utilization efficiency is low, therefore develops novel high efficiency composition light and urge
Change the emphasis that material is current photocatalysis field research.
It is well known that carbon nitrence (g-C3N4) be a kind of non-metal semiconductive photochemical catalyst, it can be applied to decompose water and
Organic pollutant.Recent a large amount of g-C3N4The composite material of semiconductor light-catalyst and silver-based is reported, national inventing patent
201811187940.0 201610332673.6,201510615287.3 report g-C3N4The preparation side of semiconductor light-catalyst
Method and application in photocatalysis field.
g-C3N4Low toxicity, stability is high and suitable forbidden bandwidth, visible light can be efficiently used, and by g-C3N4As
The reinforced phase of the modification of other catalysis materials.But single g-C3N4Light degradation property under photochemical catalyst visible light conditions
It is not high, due to its photo-generate electron-hole pairs coincidence rate is high and quantum efficiency is low, limit its answering in photocatalysis field
With.
Summary of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of carbon nitrence-zinc sulphide (g-C3N4/
ZnS) composite nano materials, specific technical solution are as follows:
A kind of carbon nitrence-zinc sulphide composite nano materials, the granularity of the composite nano materials are 30-100nm, carbon nitrence
Mass content be 5-25%, surplus is zinc sulphide.
The second object of the present invention is to provide the preparation method of above-mentioned carbon nitrence-zinc sulphide composite nano materials, specific skill
Art scheme is as follows:
A kind of preparation method of the carbon nitrence-zinc sulphide composite nano materials, comprising the following steps: zinc source is dissolved in second
Alcohol solution, then by g-C3N4Above-mentioned solution is added in nanometer sheet and surfactant, and sulphur source is added dropwise extremely in 1~2h of ultrasonic disperse
Precipitating completely, mixed liquor is transferred in stainless steel cauldron, be placed in a vacuum drying oven in 160~180 DEG C keep the temperature 16~
For 24 hours, it is cooled to room temperature；After reaction product is centrifugated, is washed 1~3 time with deionized water and dehydrated alcohol, finally existed respectively
70-90 DEG C of 8~12h of vacuum drying, obtains the carbon nitrence/zinc sulphide composite nano materials.
Preferably, the ethanol water is V by volumeEthyl alcohol:VDeionized water=1:0.5~2 are formulated；The zinc source is
Zn(AC)2、Zn(NO3)2Or Zn (SO4)2, it is 24.8~55.0g/L with the mass volume ratio in the ethanol water；The g-
C3N4Mass volume ratio in nanometer sheet and the ethanol water is 1~5g/L；The surfactant is cetyl diethyl
Mass volume ratio in base ammonium bromide, polyethylene glycol or lauryl sodium sulfate, with the ethanol water is 0.4~1.2g/
L；The sulphur source is sodium sulfide solution, ammonium sulfide is molten or thiourea solution, the amount volume ratio with the substance of the ethanol water
For 50~100mmol/L.
The third object of the present invention is to provide a kind of application of above-mentioned carbon nitrence-zinc sulphide composite nano materials, specific skill
Art scheme is as follows:
Carbon nitrence-zinc sulphide the composite nano materials are applied to carbon nitrence-zinc sulphide composite photocatalyst coating, the painting
The preparation method of layer the following steps are included: by carbon nitrence-zinc sulphide composite nano materials, curing agent, filler 1~3h of ball milling, by
It is added dropwise to inorganic bond, is stirred evenly, spraying slurry is obtained；By the spraying slurry with 0.4~0.6m/s of spraying rate, gas
0.45~0.55MPa of pressure pressure sprays to substrate surface, after multistage heat treatment, washes with water, dries, obtain the carbon nitrogen
Alkene-zinc sulphide composite photocatalyst coating.
Preferably, the multistage heat treatment process is as follows: under vacuum or inert gas conditions, being heat-treated 5 at 80~120 DEG C
~10min, then in 220~300 DEG C of 10~15min of heat treatment, then in 400~450 DEG C of 30~40min of heat treatment, then with
Furnace is cooled to room temperature.
Preferably, the curing agent is MgO, CuO or ZnO nano particle of 50~100nm partial size；The filler is
SiO2, aluminium powder or Al2O3, granularity 100-200nm；The inorganic bond be 1.25~15g/L phosphate dihydrogen aluminum solution,
Water-soluble metasilicate or dobell's solution；The substrate is ceramics, glass or metal material.
Preferably, the quality of the carbon nitrence-zinc sulphide composite nano materials, curing agent, filler, inorganic bond solute
Than for 1:0.4~1.6:0.1~5:0.25~3, the inorganic bond solute is above-mentioned aluminium dihydrogen phosphate, water-soluble metasilicate
Or Boratex.
Preferably, it is empty to be applied to photocatalytic degradation under visible light conditions for the carbon nitrence-zinc sulphide composite photocatalyst coating
Gaseous state or liquid organic pollutant in gas.
It is highly preferred that the carbon nitrence-zinc sulphide composite photocatalyst painting is placed in the container containing gaseous pollutant,
Illumination 1-3h under visible light conditions.
Beneficial effects of the present invention
The present invention provides a kind of carbon nitrence-zinc sulphide composite photo-catalyst of facile syntheesis, which effectively improves
Photocatalytic degradation capability and its stability；The catalyst is applied to carbon nitrence-zinc sulphide composite photocatalyst coating, coating tool
Standby stronger Degradation Formaldehyde ability (Degradation Formaldehyde rate reaches as high as 49.5% within 3 hours), can lead in air cleaning, sewage treatment etc.
There is important application in domain, be expected to be used for large-scale industrial production.
Detailed description of the invention
Fig. 1 is carbon nitrence produced by the present invention-zinc sulphide composite photocatalyst coating EDS spectrogram.
Fig. 2 is carbon nitrence produced by the present invention-zinc sulphide composite photocatalyst coating microcosmic scanning electron microscope (SEM) photograph (SEM).
Fig. 3 is carbon nitrence produced by the present invention-zinc sulphide composite photocatalyst coating microcosmic transmission electron microscope picture (TEM).
Specific embodiment
The present invention is further described below by way of specific embodiment, as known by the technical knowledge, the present invention can also pass through it
Its scheme for not departing from the technology of the present invention feature describes, therefore all within the scope of the present invention or in the equivalent scope of the invention
Change be included in the invention.
Embodiment 1
1, carbon nitrence-zinc sulphide composite nano materials preparation
By 1.78g Zn (AC)2It is dissolved in 50mL ethanol water (V by volumeEthyl alcohol:VDeionized water=1:0.5~2 prepare and
At), then by 0.05g solid phase method prepare gained g-C3N4The cetyl diethyl ammonium bromide of nanometer sheet and 0.02g are added above-mentioned molten
Liquid after ultrasonic disperse 2h, is added dropwise sodium sulfide solution (25mL, 0.1mol/L) to precipitating completely, mixed liquor is transferred to
In the stainless steel cauldron of 100ml, it is placed in a vacuum drying oven in 160 DEG C of heat preservations for 24 hours, is cooled to room temperature.Reaction product pass through from
After heart separation, washed repeatedly 3 times with deionized water and dehydrated alcohol respectively, finally 80 DEG C of dry 10h obtain g- under vacuum conditions
C3N4/ ZnS composite nano materials.
2, carbon nitrence-zinc sulphide composite photocatalyst coating preparation
By the g-C of 0.1g3N4/ ZnS composite nano materials, 0.04g MgO nano particle (curing agent), 0.01g SiO2It (fills out
Material, granularity 100nm) after ball milling 1h, then with pipette measure 20ml phosphate dihydrogen aluminum solution (1.25g/L) be added dropwise it is above-mentioned
In mixture, spraying slurry is made in the mixture uniform stirring in mortar；By spraying slurry with spraying rate 0.5m/s, air pressure
The process conditions of pressure 0.5MPa spray to the glass substrate surface pre-processed, then carry out multistage heat treatment process processing,
It is first heat-treated 10min at 80 DEG C, 10min is then heat-treated at 220 DEG C, finally 30min is heat-treated at 400 DEG C, with furnace
It is cooled to room temperature, then will rinse 5 minutes, dry in water purification containing carbon nitrence-zinc sulphide composite photocatalyst coating substrate,
Obtain carbon nitrence/zinc sulphide composite photocatalyst coating coated in glass surface.
Embodiment 2
1, carbon nitrence-zinc sulphide composite nano materials preparation
By 2.75g Zn (NO3)2It is dissolved in 50mL ethanol water (V by volumeEthyl alcohol:VDeionized water=1:0.5~2 prepare and
At), then by 0.1g solid phase method prepare gained g-C3N4Above-mentioned solution, ultrasonic disperse 1h is added in the polyethylene glycol of nanometer sheet and 0.04g
Afterwards, ammonium sulfide solution (25mL, 0.1mol/L) is added dropwise to precipitating completely, the stainless steel that mixed liquor is transferred to 100ml is anti-
It answers in kettle, is placed in a vacuum drying oven in 160 DEG C of heat preservations for 24 hours, is cooled to room temperature.After reaction product is centrifuged, use respectively
Deionized water and dehydrated alcohol wash 3 times repeatedly, and finally 80 DEG C of dry 10h obtain g-C under vacuum conditions3N4/ ZnS composite Nano
Material.
2, carbon nitrence-zinc sulphide composite photocatalyst coating preparation
By the g-C of 0.1g3N4/ ZnS composite nano materials, 0.1g CuO nano particle (curing agent), 0.03g aluminium powder (are filled out
Material, granularity 200nm), after ball milling 1h, then 20ml water-soluble metasilicate (5g/L) is measured with pipette, above-mentioned mixing is added dropwise
In object, spraying slurry is made in the mixture uniform stirring in mortar；By spraying slurry with spraying rate 0.5m/s, atmospheric pressure
The process conditions of 0.5MPa spray to the glass substrate surface pre-processed, then carry out multistage heat treatment process processing, first exist
It is heat-treated 5min at 120 DEG C, 15min is then heat-treated at 300 DEG C, 40min, furnace cooling are finally heat-treated at 450 DEG C
To room temperature, it then will be rinsed in water purification 5 minutes containing carbon nitrence-zinc sulphide composite photocatalyst coating substrate, dry, obtain
Carbon nitrence coated in glass surface/zinc sulphide composite photocatalyst coating.
Embodiment 3
1, carbon nitrence-zinc sulphide composite nano materials preparation
By 1.24g Zn (SO4)2It is dissolved in 50mL ethanol water (V by volumeEthyl alcohol:VDeionized water=1:0.5~2 prepare and
At), then by 0.25g solid phase method prepare gained g-C3N4Above-mentioned solution is added in nanometer sheet and the lauryl sodium sulfate of 0.06g, surpasses
After sound disperses 2h, thiourea solution [CS (NH is added dropwise2)2] (10mL, 0.5mol/L) to precipitate completely, mixed liquor is shifted
Into the stainless steel cauldron of 100ml, it is placed in a vacuum drying oven in 180 DEG C of heat preservation 16h, is cooled to room temperature.Reaction product warp
After centrifuge separation, washed repeatedly 3 times with deionized water and dehydrated alcohol respectively, finally 80 DEG C of dry 10h are obtained under vacuum conditions
g-C3N4/ ZnS composite nano materials.
2, carbon nitrence-zinc sulphide composite photocatalyst coating preparation
By the g-C of 0.1g3N4/ ZnS composite nano materials, 0.16g ZnO nano particle (curing agent), 0.5g Al2O3It (fills out
Material, granularity 100nm) after ball milling 1h, then measure 20ml dobell's solution (15g/L) with pipette and said mixture is added dropwise
In, spraying slurry is made in the mixture uniform stirring in mortar；By spraying slurry with spraying rate 0.5m/s, atmospheric pressure
The process conditions of 0.5MPa spray to the glass substrate surface pre-processed, then carry out multistage heat treatment process processing, first exist
It is heat-treated 10min at 80 DEG C, 10min is then heat-treated at 220 DEG C, 30min, furnace cooling are finally heat-treated at 400 DEG C
To room temperature, it then will be rinsed in water purification 5 minutes containing carbon nitrence-zinc sulphide composite photocatalyst coating substrate, dry, obtain
Carbon nitrence coated in glass surface/zinc sulphide composite photocatalyst coating.
Fig. 1 is carbon nitrence-zinc sulphide composite photocatalyst coating EDS map, shows that product is made of C, N, Zn, S element,
Without other impurity, C:N 1:1.32, Zn:S 1:2.05 is consistent with chemical formula, it was demonstrated that carbon nitrence/zinc sulphide at
Function preparation.Fig. 2 and Fig. 3 is respectively synthetic product carbon nitrence-zinc sulphide SEM and TEM figure, as seen from the figure diameter about 40nm
Zine sulfide nano particles are grown in sheet g-C3N4On, average dimension is about 100nm.
In order to investigate the actual effect of light catalyzed coating degradation of formaldehyde, the HJC-1 type that the present invention is generallyd use using European Union
Indoor environment under environmental test chamber simulated visible light source.Using acetylacetone,2,4-pentanedione spectrophotometry (GB/T 15516-1995), selection
Gas in the 2h sampling cabin 5L detects the concentration variation of formaldehyde gas in environmental test chamber, so as to calculate carbon nitrogen
Alkene-zinc sulphide composite photocatalyst coating Photo-Catalytic Degradation of Formaldehyde efficiency, is specifically shown in Table 1.
1. carbon nitrence of table-zinc sulphide composite photocatalyst coating Photo-Catalytic Degradation of Formaldehyde efficiency (%)
From table 1 it follows that the resulting carbon nitrence of the embodiment of the present invention 3/zinc sulphide composite photocatalyst coating is to first
The degradation effect of aldehyde is best, and 3h degradation efficiency has reached 49.5%.
Claims (9)
1. a kind of carbon nitrence-zinc sulphide composite nano materials, which is characterized in that the granularity of the composite nano materials is 30-
The mass content of 100nm, carbon nitrence are 5-25%, and surplus is zinc sulphide.
2. a kind of preparation method of carbon nitrence-zinc sulphide composite nano materials according to claim 1, which is characterized in that
The following steps are included: zinc source is dissolved in ethanol water, then by g-C3N4Above-mentioned solution is added in nanometer sheet and surfactant, surpasses
Sound disperses 1~2h, and sulphur source is added dropwise to precipitating completely, mixed liquor is transferred in stainless steel cauldron, vacuum drying is placed in
In case in 160~180 DEG C keep the temperature 16~for 24 hours, be cooled to room temperature；After reaction product is centrifugated, respectively with deionized water and
Dehydrated alcohol washs 1~3 time, finally in 70-90 DEG C of 8~12h of vacuum drying, obtains the carbon nitrence/zinc sulphide composite Nano
Material.
3. the preparation method of carbon nitrence-zinc sulphide composite nano materials according to claim 2, which is characterized in that described
Ethanol water is V by volumeEthyl alcohol:VDeionized water=1:0.5~2 are formulated；The zinc source is Zn (AC)2、Zn(NO3)2Or Zn
(SO4)2, it is 24.8~55.0g/L with the mass volume ratio in the ethanol water；The g-C3N4Nanometer sheet and the second
Mass volume ratio in alcohol solution is 1~5g/L；The surfactant is cetyl diethyl ammonium bromide, polyethylene glycol
Or the mass volume ratio in lauryl sodium sulfate, with the ethanol water is 0.4~1.2g/L；The sulphur source is vulcanized sodium
Solution, ammonium sulfide are molten or thiourea solution, the amount volume ratio with the substance of the ethanol water are 50~100mmol/L.
It is applied 4. carbon nitrence-zinc sulphide composite nano materials described in claim 1 are applied to carbon nitrence-zinc sulphide composite photocatalyst
Layer, which is characterized in that the preparation method of the coating is the following steps are included: by carbon nitrence-zinc sulphide composite nano materials, solidification
Agent, filler 1~3h of ball milling, are added dropwise inorganic bond, stir evenly, obtain spraying slurry；By the spraying slurry to spray
Painting 0.4~0.6m/s of speed, 0.45~0.55MPa of atmospheric pressure spray to substrate surface, clear with water after multistage heat treatment
It washes, dry, obtain the carbon nitrence/zinc sulphide composite photocatalyst coating.
5. the method for application according to claim 4, which is characterized in that it is described multistage heat treatment process it is as follows: vacuum or
Under inert gas conditions, in 80~120 DEG C of 5~10min of heat treatment, then in 220~300 DEG C of 10~15min of heat treatment, then exist
400~450 DEG C of 30~40min of heat treatment, then cool to room temperature with the furnace.
6. the method for application according to claim 5, which is characterized in that the curing agent is 50~100nm partial size
MgO, CuO or ZnO nano particle；The filler is SiO2, aluminium powder or Al2O3, granularity 100-200nm；The inorganic bond
For the phosphate dihydrogen aluminum solution, water-soluble metasilicate or dobell's solution of 1.25~15g/L；The substrate be ceramics, glass or
Metal material.
7. the method for application according to claim 5, which is characterized in that the carbon nitrence-zinc sulphide composite nano materials,
Curing agent, filler, inorganic bond solute mass ratio be 1:0.4~1.6:0.1~5:0.25~3, the inorganic bond
Solute is above-mentioned aluminium dihydrogen phosphate, water-soluble metasilicate or Boratex.
It is urged 8. a kind of carbon nitrence as claimed in claim 4-zinc sulphide composite photocatalyst coating is applied to light under visible light conditions
Change the gaseous state or liquid organic pollutant in degradation air.
9. the method for application according to claim 8, which is characterized in that by the carbon nitrence-zinc sulphide composite photocatalyst
Painting is placed in the container containing gaseous pollutant, it is seen that illumination 1-3h under the conditions of light.
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