CN109663611A - A kind of preparation method and its fixed nitrogen application of the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon - Google Patents
A kind of preparation method and its fixed nitrogen application of the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 38
- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002356 single layer Substances 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 18
- 150000001875 compounds Chemical class 0.000 title claims description 15
- 229910052799 carbon Inorganic materials 0.000 title claims description 14
- 229910052581 Si3N4 Inorganic materials 0.000 title claims description 13
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 26
- 239000011701 zinc Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 235000019441 ethanol Nutrition 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 230000005855 radiation Effects 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 abstract 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 13
- 230000004044 response Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000002798 spectrophotometry method Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 1
- 206010027476 Metastases Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000009401 metastasis Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明属于光催化材料合成技术领域，涉及光响应型催化剂，特别涉及石墨型氮化碳（g‑C3N4）的单层改性，并与铁酸锌（ZnFe2O4）复合形成一种单层氮化碳复合铁酸锌Z型催化剂的制备方法。本发明以二氰二胺为反应原料，通过加热分解法制备石墨型氮化碳（g‑C3N4）；然后超声剥离，改性制备单层石墨型氮化碳（SL g‑C3N4）；再将Zn(NO3)2•6H2O和Fe(NO3)3•9H2O按照反应比例添加到SL g‑C3N4的超声分散液中，水热反应制备可见光响应型Z型SL g‑C3N4/ZnFe2O4复合催化剂。本发明还公开了所制备的催化剂在可见光照射件下实现光催化固氮产氨。实验结果表明，本发明所制备的催化剂具有较好的光催化固氮产氨性能，且操作简单，具有节能环保的优点，在光催化绿色合成氨方面具有很大的开发与应用前景。
The invention belongs to the technical field of photocatalytic material synthesis, and relates to a light-responsive catalyst, in particular to the single-layer modification of graphitic carbon nitride (g-C 3 N 4 ), which is compounded with zinc ferrite (ZnFe 2 O 4 ) to form A preparation method of single-layer carbon nitride composite zinc ferrite Z-type catalyst. In the present invention, dicyandiamide is used as a reaction raw material, and the graphite-type carbon nitride (g-C 3 N 4 ) is prepared by a thermal decomposition method; then ultrasonic peeling is performed, and the single-layer graphite-type carbon nitride (SL g-C 3 ) is prepared by modification. N 4 ); Zn(NO 3 ) 2 • 6H 2 O and Fe(NO 3 ) 3 • 9H 2 O were added to the ultrasonic dispersion of SL g-C 3 N 4 according to the reaction ratio, and the visible light was prepared by hydrothermal reaction Responsive Z-type SL g‑C 3 N 4 /ZnFe 2 O 4 composite catalyst. The invention also discloses that the prepared catalyst realizes photocatalytic nitrogen fixation and ammonia production under visible light irradiation. The experimental results show that the catalyst prepared by the invention has good photocatalytic nitrogen fixation and ammonia production performance, is simple to operate, has the advantages of energy saving and environmental protection, and has great development and application prospects in photocatalytic green synthesis of ammonia.
Description
Technical field
The invention belongs to catalysis material synthesis technical fields, are related to photoresponse type catalyst, in particular to graphite mould nitrogen
Change carbon (g-C3N4) it is monolayer-modified, and with zinc ferrite (ZnFe2O4) it is compounded to form a kind of compound zinc ferrite Z-type of single-layer silicon nitride carbon
The preparation method and its fixed nitrogen application of catalyst.
Background technique
In recent decades, the development of photocatalysis technology causes people and more and more pays close attention to.It is organic in photocatalytic degradation
Pollutant produces in many application fields such as hydrogen, carbon dioxide reduction, sterilization and fixed nitrogen, and photocatalysis fixed nitrogen is current photocatalysis skill
The hot spot of art area research.Photocatalysis fixed nitrogen produces a kind of ammonia synthesis technology of the ammonia as green, can solve environment (low CO simultaneously2
Discharge) and the energy (producing ammonia) problem.Relative to conventional catalyst titanium dioxide, non-metal semiconductive graphite type carbon nitride (g-
C3N4) the moderate band gap width (2.7 eV) of visible light can be absorbed with one, and there is heat-resisting and resistance toization quite outstanding
Etc. performances, thus received significant attention in many photocatalysis research fields.
Applied Catalysis B:Environmental 160-161 (2014) 89-97, reports by molten
Agent thermal method utilizes Bi2MoO6Modified g-C3N4Heterojunction structure is formed, photocatalytic activity is relative to single g- under radiation of visible light
C3N4Improve 3 times or more；But composite photo-catalyst electronics transfer mechanism prepared by the research is to be related to Z-type transferring route.
Applied Catalysis B:Environmental 202 (2017) 489-499, it was recently reported that logical by controlling
It crosses hydro-thermal one-step method and is prepared for C-TiO2/g-C3N4Nano composite photo-catalyst.The result shows that prepared nano-composite catalyst
Since the stroke of heterojunction structure effectively increases the separative efficiency of hole-electron；But metastasis involved in the research
Using C as electronics transfer intermediate, it is still not directed to all solid state Z-type transferring route.
Material engineering, 2018,9 (46): 39-45 is reported through calcination processing and precipitation reaction synthesis with Ag nanometers
Particle is the Z- type photochemical catalyst Ag of electronic media2CO3/Ag/ g-C3N4, and investigate its photocatalytic degradation RhB performance.As a result table
Bright, due to Ag nanoparticle surface ion resonance effect, Z- type heterojunction structure extends visible absorption wave-length coverage (from 450
To 670 nm), Ag2CO3/Ag/g-C3N4Sample is shown than pure Ag2CO3And g-C3N4Stronger photocatalytic activity.But it is not directed to
g-C3N4Pattern control, and be not directed to reduction fixed nitrogen research.
However, g-C3N4In the practical application of catalytic field, there are the separative efficiency of photo-generate electron-hole slowly and
Relatively narrow visible light-responded range problem.Therefore, the composite photo-catalyst for designing high activity becomes the research weight of photocatalysis field
Point, composite photo-catalyst design are to promote one of the important modification approach of photocatalytic activity.Pass through g-C3N4Pattern control and
High activity semiconductor material with narrow band gap is composite modified, is to promote the absorption of light and turning for light excitation hole-electron
One of effective way of shifting, to reduce photohole-electronics recombination rate.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is disclose a kind of g-C3N4It is monolayer-modified
And compound zinc ferrite (ZnFe2O4) form the preparation method of all solid state Z- type visible-light response type composite photo-catalyst, and by institute
The catalyst of preparation is applied to photo catalytic reduction fixed nitrogen.
The preparation method of the flower-shaped catalyst of photoresponse type disclosed in this invention, using dicyanodiamine as reaction raw materials, heating
Decomposition method prepares graphite type carbon nitride (g-C3N4)；Then by ultrasound removing, modification prepares mono-layer graphite type carbonitride (SL g-
C3N4)；Again by Zn (NO3)2•6H2O and Fe (NO3)3•9H2O is added to SL g-C according to reaction ratio3N4Ultrasonic disperse liquid
In, visible-light response type Z-type SL g-C is prepared by hydro-thermal reaction3N4/ZnFe2O4Composite catalyst；Finally, thus catalyst
Realize that photocatalysis fixed nitrogen produces ammonia under radiation of visible light part.
A kind of compound zinc ferrite Z-type of single-layer silicon nitride carbon (Z-type SL g-C3N4/ZnFe2O4) catalyst preparation method, including
Following steps:
(A) g-C3N4Preparation: dicyanodiamine is laid in the silica crucible of capping, with 10 DEG C of min-1It is warming up to 600
DEG C, 2 h are heated under nitrogen protection, are then cooled to room temperature, and being ground into powder, it is spare to collect；
(B) SL g-C3N4Preparation: by g-C3N4It is scattered in Organic Alcohol, 1~24 h of ultrasound under 50~150Hz frequency, is centrifuged
It collects, 60 °C of dry 12h;Wherein, the g-C3N4The ratio of quality (mg) and Organic Alcohol volume (mL) is 1/1~100, preferably
1/10；The Organic Alcohol is methanol, ethyl alcohol, ethylene glycol or isopropanol, preferably isopropanol；The preferred 100Hz of supersonic frequency；When ultrasonic
Between preferred 8h；
(C) SL g-C3N4/ZnFe2O4Preparation: under agitation, by SL g-C3N4It is scattered in Organic Alcohol, stirring 0.5~
12h obtains SL g-C3N4Alcohol dispersion liquid；Wherein, SL g-C3N4The ratio of quality (mg) and alcohol volume (mL) is 1/1~10, preferably
1/2；The Organic Alcohol is methanol, ethyl alcohol, ethylene glycol or isopropanol, preferably ethylene glycol；The preferred 2h of mixing time；
By Zn (NO3)2•6H2O and Fe (NO3)3•9H2O is added sequentially to SL g-C3N4Alcohol dispersion liquid in, stirring 1~shape for 24 hours
At uniform dispersion, it is 7~13 that ammonium hydroxide, which is added dropwise, and adjusts the pH value of dispersion liquid, and mixed liquor is then transferred to high-temperature high-pressure reaction kettle
In, 120~220 DEG C of reactions 8~for 24 hours；Wherein, the Zn (NO3)2•6H2O and Fe (NO3)3•9H2Molar ratio 0.5:1~2 of O:
1, preferably 1:1；Zn (the NO3)2•6H2O and SL g-C3N4Mass ratio be 0.1:1~1.23:1, preferably 0.246:1；Stirring
Time preferred 12h；PH value preferably 11；It is preferred that 180 DEG C of reaction 12h；
(D) reaction terminates, cooled to room temperature, is cleaned products therefrom with the ethanol water that volume ratio is 50%, then very
60 DEG C of drying 12h of empty constant temperature, obtain visible-light response type SL g-C3N4/ZnFe2O4Catalyst.
Blank control test of the invention is not add SL g-C3N4It under sample condition, repeats the above steps, is made
ZnFe2O4Sample.
A further object of the invention is by obtained SL g-C3N4/ZnFe2O4It is catalyzed under the conditions of radiation of visible light
Fixed nitrogen produces ammonia.
Under normal temperature and pressure conditions, in the methanol aqueous solution of 500mL, prepared catalyst is added, ultrasound is to ensure to urge
Agent is uniformly dispersed.Under illumination condition, nitrogen (N is passed through into dispersion liquid with certain aeration rate2) certain time, it takes
Sample, centrifuge separation, takes its clear liquid, is measured using Berthelot spectrophotometry and produces ammonia efficiency.
Wherein methanol aqueous solution concentration can be 0.001~1.0 mol/L, preferably 0.02 mol/L；
The volume ratio of catalyst quality and reaction solution can be 0.1~1g/L, preferably 0.2g/L；
The aeration rate of nitrogen can be 10~200 mL/min, preferably 100mL/min.
Dicyanodiamine (C used in the present invention2H4N4), zinc nitrate hexahydrate (Zn (NO3)2•6H2O), Fe(NO3)39H2O
(Fe (NO3)3•9H2O), ethyl alcohol, methanol, ethylene glycol and isopropanol, Sinopharm Chemical Reagent Co., Ltd..
Beneficial effect
The present invention is by conventional g-C3N4Ultrasound removing is SL g-C3N4, and compound ZnFe2O4Successfully prepare visible-light response type Z-type
SL g-C3N4/ZnFe2O4Catalyst, and the catalyst is applied to photocatalysis fixed nitrogen and produces ammonia.The experimental results showed that prepared urge
There is agent preferable photocatalysis fixed nitrogen to produce ammonia performance, and easy to operate, have popularizing action, tool to photocatalysis green syt ammonia
There is the advantages of energy conservation and environmental protection.
Detailed description of the invention
Fig. 1 SL g-C3N4/ZnFe2O4Electron-microscope scanning (SEM) shape appearance figure；
Fig. 2 SL g-C3N4/ZnFe2O4Electric charge transfer route and mechanism of action figure.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited to following embodiments.
Embodiment 1
(1) 2 g dicyanodiamines are laid in the silica crucible of capping, then with 10 DEG C of min-1It is warming up to 600 DEG C, and
2 h are heated under nitrogen protection.End of reaction waits for that sample is cooled to room temperature, and is ground into powdered g-C by agate mortar3N4；
Then g-C prepared by 5mg will be taken3N4It is added in 500 mL methanol, 50Hz ultrasound 1h under normal temperature condition, 60 after being collected by centrifugation
°C dry 12 h, are made SL g-C3N4-1。
(2) under agitation, by SL g-C prepared by 100mg3N4- 1 is added in 1000mL methanol, stirring
0.5h；Then 10.0 mg Zn (NO are successively added3)2•6H2O and 27.2 mg Fe (NO3)3•9H2O continues after stirring 1h, passes through
It is 7 that ammonium hydroxide, which is added dropwise, and adjusts the pH value of dispersion liquid；Then mixed liquor is transferred in high-temperature high-pressure reaction kettle, it is anti-under the conditions of 120 DEG C
Answer 8h；Reaction terminates, cooled to room temperature, and products therefrom is washed 3 times by the ethanol water for being 50% with volume ratio, then
60 DEG C of drying 12h under vacuum conditions, obtain visible-light response type SL g-C3N4/ZnFe2O4- 1 sample.
(3) under normal temperature and pressure conditions, the SL g- of 50 mg is added in Xiang 500mL methanol aqueous solution (0.001mol/L)
C3N4/ZnFe2O4- 1 catalyst, ultrasonic 10min.Under the conditions of radiation of visible light, nitrogen is passed through with 10mL/min.Reaction 120
Min takes its clear liquid, and Berthelot spectrophotometry measurement is used to produce ammonia efficiency as 0.23 μm of ol/L/min.
Embodiment 2
(1) 2 g dicyanodiamines are laid in the silica crucible of capping, then with 10 DEG C of min-1It is warming up to 600 DEG C, and
2 h are heated under nitrogen protection.End of reaction waits for that sample is cooled to room temperature, and is ground into powdered g-C by agate mortar3N4；
Then g-C prepared by 25mg will be taken3N4It is added in 500 mL ethyl alcohol, 60Hz ultrasound 2h under normal temperature condition, 60 after being collected by centrifugation
°C dry 12 h, are made SL g-C3N4-2。
(2) under agitation, by SL g-C prepared by 100mg3N4- 2 are added in 500mL ethyl alcohol, stir 2h；So
14.98 mg Zn (NO are successively added afterwards3)2•6H2O and 22.1 mg Fe (NO3)3•9H2O continues after stirring 4h, by the way that ammonia is added dropwise
The pH value that water adjusts dispersion liquid is 8；Then mixed liquor is transferred in high-temperature high-pressure reaction kettle, reacts 12h under the conditions of 140 DEG C；
Reaction terminates, cooled to room temperature, is washed products therefrom 3 times with the ethanol water that volume ratio is 50%, then in vacuum
Under the conditions of 60 DEG C of drying 12h, obtain visible-light response type SL g-C3N4/ZnFe2O4- 2 samples.
(3) under normal temperature and pressure conditions, the SL g- of 100 mg is added in Xiang 500mL methanol aqueous solution (0.001mol/L)
C3N4/ZnFe2O4- 2 catalyst, ultrasonic 10min.Under the conditions of radiation of visible light, nitrogen is passed through with 40mL/min.Reaction 120
Min takes its clear liquid, and Berthelot spectrophotometry measurement is used to produce ammonia efficiency as 0.45 μm of ol/L/min.
Embodiment 3
(1) 2 g dicyanodiamines are laid in the silica crucible of capping, then with 10 DEG C of min-1It is warming up to 600 DEG C, and
2 h are heated under nitrogen protection.End of reaction waits for that sample is cooled to room temperature, and is ground into powdered g-C by agate mortar3N4；
Then g-C prepared by 50 mg will be taken3N4It is added in 500 mL ethylene glycol, 80Hz ultrasound 4h under normal temperature condition, after being collected by centrifugation
In 60 °C of dry 12 h, SL g-C is made3N4-3。
(2) under agitation, by SL g-C prepared by 100mg3N4- 3 are added in 200mL ethylene glycol, stir 8h；
Then 20.05 mg Zn (NO are successively added3)2•6H2O and 17.1 mg Fe (NO3)3•9H2O continues after stirring 8h, passes through dropwise addition
The pH value that ammonium hydroxide adjusts dispersion liquid is 10；Then mixed liquor is transferred in high-temperature high-pressure reaction kettle, is reacted under the conditions of 160 DEG C
16h；Reaction terminates, cooled to room temperature, washs products therefrom 3 times with the ethanol water that volume ratio is 50%, then exists
The lower 60 DEG C of drying 12h of vacuum condition, obtains visible-light response type SL g-C3N4/ZnFe2O4- 3 samples.
(3) under normal temperature and pressure conditions, the SL g- of 150 mg is added in Xiang 500mL methanol aqueous solution (0.001mol/L)
C3N4/ZnFe2O4- 3 catalyst, ultrasonic 10min.Under the conditions of radiation of visible light, nitrogen is passed through with 80mL/min.Reaction 120
Min takes its clear liquid, and Berthelot spectrophotometry measurement is used to produce ammonia efficiency as 0.63 μm of ol/L/min.
Embodiment 4
(1) 2 g dicyanodiamines are laid in the silica crucible of capping, then with 10 DEG C of min-1It is warming up to 600 DEG C, and
2 h are heated under nitrogen protection.End of reaction waits for that sample is cooled to room temperature, and is ground into powdered g-C by agate mortar3N4；
Then g-C prepared by 50 mg will be taken3N4It is added in 500 mL isopropanols, 100Hz ultrasound 8h under normal temperature condition, after being collected by centrifugation
In 60 °C of dry 12 h, SL g-C is made3N4-4。
(2) under agitation, by SL g-C prepared by 100mg3N4- 4 are added in 200mL ethylene glycol, stir 2h；
Then 24.6 mg Zn (NO are successively added3)2•6H2O and 13.6 mg Fe (NO3)3•9H2O continues after stirring 12h, passes through dropwise addition
The pH value that ammonium hydroxide adjusts dispersion liquid is 11；Then mixed liquor is transferred in high-temperature high-pressure reaction kettle, is reacted under the conditions of 180 DEG C
12h；Reaction terminates, cooled to room temperature, washs products therefrom 3 times with the ethanol water that volume ratio is 50%, then exists
The lower 60 DEG C of drying 12h of vacuum condition, obtains visible-light response type SL g-C3N4/ZnFe2O4- 4 samples.
(3) under normal temperature and pressure conditions, the SL g- of 100 mg is added in Xiang 500mL methanol aqueous solution (0.001mol/L)
C3N4/ZnFe2O4- 4 catalyst, ultrasonic 10min.Under the conditions of radiation of visible light, nitrogen is passed through with 100mL/min.Reaction 120
Min takes its clear liquid, and Berthelot spectrophotometry measurement is used to produce ammonia efficiency as 1.02 μm of ol/L/min.
Embodiment 5
(1) 2 g dicyanodiamines are laid in the silica crucible of capping, then with 10 DEG C of min-1It is warming up to 600 DEG C, and
2 h are heated under nitrogen protection.End of reaction waits for that sample is cooled to room temperature, and is ground into powdered g-C by agate mortar3N4；
Then g-C prepared by 200 mg will be taken3N4It is added in 500 mL ethyl alcohol, 100Hz ultrasound 16h under normal temperature condition, after being collected by centrifugation
In 60 °C of dry 12 h, SL g-C is made3N4-5。
(2) under agitation, by SL g-C prepared by 100mg3N4- 5 are added in 100mL isopropanol, stir 4h；
Then 50.2 mg Zn (NO are successively added3)2•6H2O and 10.2 mg Fe (NO3)3•9H2O continues after stirring 18h, passes through dropwise addition
The pH value that ammonium hydroxide adjusts dispersion liquid is 9；Then mixed liquor is transferred in high-temperature high-pressure reaction kettle, is reacted under the conditions of 200 DEG C
16h；Reaction terminates, cooled to room temperature, washs products therefrom 3 times with the ethanol water that volume ratio is 50%, then exists
The lower 60 DEG C of drying 12h of vacuum condition, obtains visible-light response type SL g-C3N4/ZnFe2O4- 5 samples.
(3) under normal temperature and pressure conditions, the SL g- of 200 mg is added in Xiang 500mL methanol aqueous solution (0.001mol/L)
C3N4/ZnFe2O4- 5 catalyst, ultrasonic 10min.Under the conditions of radiation of visible light, nitrogen is passed through with 150mL/min.Reaction 120
Min takes its clear liquid, and Berthelot spectrophotometry measurement is used to produce ammonia efficiency as 0.85 μm of ol/L/min.
Embodiment 6
(1) 2 g dicyanodiamines are laid in the silica crucible of capping, then with 10 DEG C of min-1It is warming up to 600 DEG C, and
2 h are heated under nitrogen protection.End of reaction waits for that sample is cooled to room temperature, and is ground into powdered g-C by agate mortar3N4；
Then g-C prepared by 500 mg will be taken3N4Be added in 500 mL methanol, under normal temperature condition 150Hz ultrasound for 24 hours, after being collected by centrifugation
In 60 °C of dry 12 h, SL g-C is made3N4-6。
(2) under agitation, by SL g-C prepared by 100mg3N4- 6 are added in 100mL methanol, stir 12h；
Then 123.2 mg Zn (NO are successively added3)2•6H2O and 6.8mg Fe (NO3)3•9H2O passes through dropwise addition after continuing stirring for 24 hours
The pH value that ammonium hydroxide adjusts dispersion liquid is 13；Then mixed liquor is transferred in high-temperature high-pressure reaction kettle, is reacted under the conditions of 220 DEG C
24h；Reaction terminates, cooled to room temperature, washs products therefrom 3 times with the ethanol water that volume ratio is 50%, then exists
The lower 60 DEG C of drying 12h of vacuum condition, obtains visible-light response type SL g-C3N4/ZnFe2O4- 6 samples.
(3) under normal temperature and pressure conditions, the SL g- of 500 mg is added in Xiang 500mL methanol aqueous solution (0.001mol/L)
C3N4/ZnFe2O4- 6 catalyst, ultrasonic 10min.Under the conditions of radiation of visible light, nitrogen is passed through with 200 mL/min.Reaction 120
Min takes its clear liquid, and Berthelot spectrophotometry measurement is used to produce ammonia efficiency as 0.61 μm of ol/L/min.
Blank Example
(1) under agitation, 24.6 mg Zn (NO are successively added into 200mL ethylene glycol3)2•6H2O and 13.6 mg Fe
(NO3)3•9H2O, after being kept stirring 12h, the pH value that dispersion liquid is adjusted by the way that ammonium hydroxide is added dropwise is 11；Then mixed liquor is transferred to
In high-temperature high-pressure reaction kettle, 12h is reacted under the conditions of 180 DEG C；Reaction terminates, cooled to room temperature, the second for being 50% with volume ratio
Alcohol solution washs products therefrom 3 times, and then 60 DEG C of drying 12h under vacuum conditions, obtain ZnFe2O4Sample.
(2) under normal temperature and pressure conditions, the ZnFe of 100 mg is added in Xiang 500mL methanol aqueous solution (0.001mol/L)2O4
Sample, ultrasonic 10min.Under the conditions of radiation of visible light, nitrogen is passed through with 100mL/min.120 min are reacted, its clear liquid is taken, adopts
Being measured with Berthelot spectrophotometry and producing ammonia efficiency is 0.13 μm of ol/L/min.
Fig. 1 is SL g-C3N4/ZnFe2O4SEM figure, particle ZnFe2O4Even particulate dispersion is in stratiform SL g-C3N4Table
Face is in interlayer；
Fig. 2 shows that traditional electric charge transfer route cannot achieve photocatalysis fixed nitrogen and produce the effect (Model I) of ammonia, and passes through Z-type
Transferring route, it can be achieved that photocatalysis fixed nitrogen produce ammonia performance (Model II).
The result shows that g-C3N4Through ultrasound removing after with ZnFe2O4Compound dual modified prepared Z-type SL g-C3N4/
ZnFe2O4There is catalyst excellent photo catalytic reduction fixed nitrogen to produce ammonia performance.Under visible light illumination, 100mg is added into system to urge
Agent is passed through nitrogen with 100mL/min, reacts 120min, and photo catalytic reduction fixed nitrogen produces ammonia efficiency up to 1.02 μm of ol/L/min.
So Z-type SL g-C prepared by the present invention3N4/ZnFe2O4Catalyst has very big in terms of photocatalysis green syt ammonia
Exploitation and application prospect.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon, which comprises the steps of:
(A) g-C3N4Preparation: dicyanodiamine is laid in the silica crucible of capping, with 10 DEG C of min-1It is warming up to 600
DEG C, 2 h are heated under nitrogen protection, are then cooled to room temperature, and being ground into powder, it is spare to collect；
(B) SL g-C3N4Preparation: by g-C3N4It is scattered in Organic Alcohol, 1~24 h of ultrasound under 50~150Hz frequency, centrifugation is received
Collection, 60 °C of dry 12h;Wherein, the g-C3N4The ratio of quality and Organic Alcohol volume is 1 mg/1~100 mL；It is described organic
Alcohol is methanol, ethyl alcohol, ethylene glycol or isopropanol；
(C) SL g-C3N4/ZnFe2O4Preparation: under agitation, by SL g-C3N4It is scattered in Organic Alcohol, stirring 0.5~
12h obtains SL g-C3N4Alcohol dispersion liquid；Wherein, the SL g-C3N4The ratio of quality and alcohol volume is 1 mg/1~10 mL；Institute
Stating Organic Alcohol is methanol, ethyl alcohol, ethylene glycol or isopropanol；
By Zn (NO3)2•6H2O and Fe (NO3)3•9H2O is added sequentially to SL g-C3N4Alcohol dispersion liquid in, stirring 1~formed for 24 hours
Uniform dispersion, it is 7~13 that ammonium hydroxide, which is added dropwise, and adjusts the pH value of dispersion liquid, and mixed liquor is then transferred to high-temperature high-pressure reaction kettle
In, 120~220 DEG C of reactions 8~for 24 hours；Wherein, the Zn (NO3)2•6H2O and Fe (NO3)3•9H2Molar ratio 0.5:1~2 of O:
1, the Zn (NO3)2•6H2O and SL g-C3N4Mass ratio be 0.1:1~1.23:1；
(D) reaction terminates, cooled to room temperature, is cleaned products therefrom with the ethanol water that volume ratio is 50%, then very
60 DEG C of drying 12h of empty constant temperature to get.
2. the preparation method of the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon according to claim 1, it is characterised in that: step
Suddenly (B) g-C3N4The ratio of quality and Organic Alcohol volume is the mL of 1 mg/10, and the Organic Alcohol is isopropanol, supersonic frequency
100Hz, ultrasonic time 8h.
3. the preparation method of the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon according to claim 1, it is characterised in that: step
Suddenly (C) the SL g-C3N4The ratio of quality and alcohol volume is the mL of 1 mg/2, and the Organic Alcohol is ethylene glycol, stirs 2h.
4. the preparation method of the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon according to claim 1, it is characterised in that: step
Suddenly (C) Zn (NO3)2•6H2O and Fe (NO3)3•9H2The molar ratio 1:1 of O；Zn (the NO3)2•6H2O and SL g-C3N4Matter
Amount is than being 0.246:1.
5. the preparation method of the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon according to claim 1, it is characterised in that: step
Suddenly (C) is described by Zn (NO3)2•6H2O and Fe (NO3)3•9H2O is added sequentially to SL g-C3N4Alcohol dispersion liquid in, stir 12h shape
At uniform dispersion, it is 11 that ammonium hydroxide, which is added dropwise, and adjusts the pH value of dispersion liquid.
6. the preparation method of the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon according to claim 1, it is characterised in that: step
Suddenly (C) is described is transferred to mixed liquor in high-temperature high-pressure reaction kettle, 180 DEG C of reaction 12h.
7. the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon made from -6 any the methods according to claim 1.
8. a kind of application of the compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon described in claim 7, it is characterised in that: will be made
The compound zinc ferrite Z-type catalyst of single-layer silicon nitride carbon obtained is catalyzed fixed nitrogen under the conditions of radiation of visible light and produces ammonia.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961135A (en) * | 2019-12-12 | 2020-04-07 | 南京理工大学 | Preparation method of graphite-like phase carbon nitride-based composite nano semiconductor material |
| CN111644188A (en) * | 2020-02-29 | 2020-09-11 | 浙江工业大学 | ZnCo2O4/g-C3N4Composite material, preparation and application thereof |
| CN112675891A (en) * | 2020-12-23 | 2021-04-20 | 西安交通大学 | High-dispersion magnetic nano photocatalyst and preparation method thereof |
| CN113976155A (en) * | 2021-10-09 | 2022-01-28 | 江苏大学 | Preparation method of porous carbon nitride-ferrite composite catalyst with nitrogen/oxygen-containing double defect structure and application of photocatalyst in nitrogen fixation |
| CN115283003A (en) * | 2022-10-10 | 2022-11-04 | 河北海鹰环境安全科技股份有限公司 | A kind of method for preparing ozone catalyst by microwave method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941671A (en) * | 2015-05-29 | 2015-09-30 | 郑州大学 | Zinc ferrite/bismuth oxyiodide magnetic composite visible photocatalyst and preparation method thereof |
| CN105597764A (en) * | 2016-03-09 | 2016-05-25 | 中国科学院地球环境研究所 | Preparation method of carbon quantum dot/zinc ferrite composite photocatalytic materials |
| CN105817253A (en) * | 2016-04-12 | 2016-08-03 | 中国计量大学 | Method for preparing graphite phase carbon nitride nanosheet/titania nanotube array photocatalysis material |
| CN106378171A (en) * | 2016-08-17 | 2017-02-08 | 浙江工业大学 | Preparation method of a magnetic ZnFe2O4/g-C3N4 composite photocatalytic material |
| CN106694016A (en) * | 2016-11-24 | 2017-05-24 | 陕西科技大学 | A kind of g-C3N4/Bi2O3 composite powder and its preparation method and application |
| CN108772095A (en) * | 2018-07-13 | 2018-11-09 | 中国计量大学 | A kind of preparation method of efficient degradation antibiotic visible light catalytic composite material |
-
2018
- 2018-11-30 CN CN201811452488.6A patent/CN109663611B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941671A (en) * | 2015-05-29 | 2015-09-30 | 郑州大学 | Zinc ferrite/bismuth oxyiodide magnetic composite visible photocatalyst and preparation method thereof |
| CN105597764A (en) * | 2016-03-09 | 2016-05-25 | 中国科学院地球环境研究所 | Preparation method of carbon quantum dot/zinc ferrite composite photocatalytic materials |
| CN105817253A (en) * | 2016-04-12 | 2016-08-03 | 中国计量大学 | Method for preparing graphite phase carbon nitride nanosheet/titania nanotube array photocatalysis material |
| CN106378171A (en) * | 2016-08-17 | 2017-02-08 | 浙江工业大学 | Preparation method of a magnetic ZnFe2O4/g-C3N4 composite photocatalytic material |
| CN106694016A (en) * | 2016-11-24 | 2017-05-24 | 陕西科技大学 | A kind of g-C3N4/Bi2O3 composite powder and its preparation method and application |
| CN108772095A (en) * | 2018-07-13 | 2018-11-09 | 中国计量大学 | A kind of preparation method of efficient degradation antibiotic visible light catalytic composite material |
Non-Patent Citations (3)
| Title |
|---|
| HUANX IN ZHAO ET AL.: "Atomic single layer graphitic-C3N4：fabrication and its high photocatalytic performance under visible light irradiation", 《RSC ADVANCES》 * |
| LONG CHEN ET AL.: "Facile synthesis of highly efficient graphitic-C3N4/ZnFe2O4 heterostructures enhanced visible-light photocatalysis for spiramycin degradation", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 * |
| YANJUAN WANG ET AL.: "In situ construction o f Z-scheme g-C3N4/Mg1.1Al0.3Fe0.2O1.7 nanorod heterostructures with high N2 photo fixation ability under visible light", 《RSC ADVANCES》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961135A (en) * | 2019-12-12 | 2020-04-07 | 南京理工大学 | Preparation method of graphite-like phase carbon nitride-based composite nano semiconductor material |
| CN111644188A (en) * | 2020-02-29 | 2020-09-11 | 浙江工业大学 | ZnCo2O4/g-C3N4Composite material, preparation and application thereof |
| CN112675891A (en) * | 2020-12-23 | 2021-04-20 | 西安交通大学 | High-dispersion magnetic nano photocatalyst and preparation method thereof |
| CN113976155A (en) * | 2021-10-09 | 2022-01-28 | 江苏大学 | Preparation method of porous carbon nitride-ferrite composite catalyst with nitrogen/oxygen-containing double defect structure and application of photocatalyst in nitrogen fixation |
| CN113976155B (en) * | 2021-10-09 | 2024-03-19 | 江苏大学 | Preparation method and light nitrogen fixation application of porous carbon nitride-ferrite composite catalyst with nitrogen/oxygen double defect structure |
| CN115283003A (en) * | 2022-10-10 | 2022-11-04 | 河北海鹰环境安全科技股份有限公司 | A kind of method for preparing ozone catalyst by microwave method |
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