CN108033432A - A kind of cage structure material g-C3N4Preparation method and applications - Google Patents
A kind of cage structure material g-C3N4Preparation method and applications Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 15
- 239000000243 solution Substances 0.000 claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 239000002091 nanocage Substances 0.000 claims abstract description 3
- 239000012670 alkaline solution Substances 0.000 claims abstract 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 176
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 230000008092 positive effect Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 82
- 239000011787 zinc oxide Substances 0.000 description 41
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 235000013904 zinc acetate Nutrition 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017665 NH4HF2 Inorganic materials 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- 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
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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
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- 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
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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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Abstract
The present invention relates to a kind of cage structure material g C3N4Preparation method and applications.Using ZnO as hard template, the C using melamine as precursor synthesis nanocage structure3N4Material, and acid solution or alkaline solution are used as etching agent.The positive effect of the present invention is:ZnO is used first as template, and melamine is presoma, and hydrochloric acid solution or sodium hydroxid aqueous solution are etching agent, and the g C of caged pattern are obtained using uniformly baking mixed simple preparation method3N4Material.
Description
Technical field
The present invention relates to a kind of cage structure material g-C3N4Preparation method and applications.
Background technology
In recent years, a kind of nonmetallic organic polymer semiconductor functional material --- class graphite phase carbon nitride(g-C3N4)By
In it with relatively low energy gap(Eg=2.70 eV), higher chemical stability, it is easily modified, prepare it is simple, to visible ray
Response is good and has the advantages that higher photocatalysis performance, is widely paid close attention to.But g-C prepared by current usual method3N4
Block random pattern is presented, specific surface area and pore volume are relatively low, strongly limit its application in most of fields.
At present, people's generally use hard template preparation method, using melamine, dicyandiamide or urea as preparation g-C3N4's
Presoma, by introducing template in heat polymerization process, to control g-C3N4Microscopic appearance, so as to synthesize with Gao Bibiao
Face and the mesoporous g-C of pore volume3N4.Commonly used more hard mould agent includes silica, and SBA-15 and KIT-6 etc., pass through
From different C3N4Presoma combines, and prepares the g-C with loose structure3N4, g-C is greatly improved3N4Specific surface area, increase
Electronics captures site and is conducive to the separation of photo-generated carrier, so as to improve photocatalysis performance and widen it in other catalysis
The application in oxidation field.Such as Wang Xing morning seminars are using having shell structurre SiO2Prepared for hard mould agent with hollow
The bionical g-C of structure3N4Nanoparticle, and substantially increase the efficiency of its Photocatalyzed Hydrogen Production(Nature
Communications, 2012,3 (4):1139.Markus Antonietti seminars are utilized with regular pore canal structure
SBA-15 nanometer rods are template, are evaporated after uniformly being mixed with cyanamide presoma, the thermal polymerization formation g-C at 550 DEG C3N4@
SBA-15 composite nano materials, finally using NH4HF2Template SBA-15 is removed to prepare mesoporous g-C3N4Nanometer rods.But current institute
The template of use is to g-C3N4Affinity it is poor, be not easy to form meso-hole structure.
ZnO is as amphoteric oxide, usually as a kind of Photocatalysis Function Material of excellent performance, due to its energy gap
It is larger, apply the photocatalytic degradation organic matter under ultraviolet excitation more.At present, most researcher is relatively narrow with energy gap by it
Semi-conducting material is compounded to form compound dissimilar materials, to widen its application in photocatalytic degradation field significantly.For example, publication number
A kind of ZnO/ g-C for preparing core shell structure are disclosed for the patent of CN106430286A3N4The method of composite material, using urea
It is soluble in water at room temperature for presoma, then add Zinc oxide nanoparticle and uniformly mix, then 450 DEG C of 2 h of roasting, obtain
The ZnO/ g-C of faint yellow core shell structure3N4Composite material.But applications of the ZnO in terms of template was not reported so far.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of technique is simple, are easily formed the g-C of cage structure3N4's
Preparation method.
The main technical schemes of the present invention are using ZnO as hard template, using melamine as precursor synthesis nanocage knot
The C of structure3N4Material.
Specifically include following steps:Melamine presoma is soluble in water, it is vigorously stirred to obtain in 50 DEG C -80 DEG C
Settled solution, then ZnO nano particle is scattered in ethanol, it is slowly added dropwise into above-mentioned solution, and be stirred by ultrasonic uniform.Then lead to
Cross vacuum distillation and obtain white solid powder, finally drying in 80 DEG C of -100 DEG C of baking ovens by it.By the white powder of above-mentioned acquisition
End grinding is uniform, then shifts and 500 DEG C of -550 DEG C of roasting 1-3 h of Muffle furnace are placed in crucible.Then with hydrochloric acid solution or
Sodium hydrate aqueous solution etches ZnO templates, finally obtains the g-C of faint yellow caged pattern3N4Material.
As further preferred:StepMiddle presoma melamine and the mass ratio of deionized water are 1:25-1:50,
It is completely dissolved under the conditions of 50 DEG C -80 DEG C.
As further preferred:StepMiddle ZnO templates and melamine mass ratio are 1:1-10:1.
As further preferred:StepThe concentration of middle hydrochloric acid solution or sodium hydrate aqueous solution is 3-5 mol/L, excellent
The hydrochloric acid solution of choosing or the concentration of sodium hydrate aqueous solution are 2-4 mol/L.
Above-mentioned used ZnO templates are prepared using forced hydrolysis method:Zinc acetate is dissolved in diethylene glycol (DEG) solvent, is added
Enter a certain amount of water, then above-mentioned solution is warming up under violent stirring under certain temperature and reacts 0.5-1 h.System is taken
After going out cooling, ZnO is dried to obtain for 80 DEG C -100 DEG C after being washed three times with ethanol.
As further preferred:StepThe concentration of acetic acid zinc solution is 0.06-0.2 mol/L.
As further preferred:StepH2O and Zn2+The amount ratio of material be 0-20.
As further preferred:StepReaction temperature is 170-210 DEG C.
The positive effect of the present invention is:ZnO is used first as template, and melamine is presoma, hydrochloric acid solution or hydrogen-oxygen
It is etching agent that aqueous solution is received in change, and the g-C of caged pattern is obtained using the simple preparation method of uniform mixing-roasting3N4Material.
Brief description of the drawings
Fig. 1 (a) is g-C prepared by usual method3N4, Fig. 1 (b) is prepared by embodiment 1, embodiment 7 and embodiment 8
ZnO, Fig. 1 (c) are g-C prepared by aqueous hydrochloric acid solution etching3N4The g- prepared with Fig. 1 (d) sodium hydrate aqueous solutions etching
C3N4TEM schemes.
Fig. 2 is ZnO, the g-C of usual method preparation prepared by embodiment 1, embodiment 7 and embodiment 83N4, aqueous hydrochloric acid solution
G-C prepared by etching and sodium hydrate aqueous solution etching3N4XRD diagram.
Fig. 3 is ZnO, the g-C of usual method preparation prepared by embodiment 1, embodiment 7 and embodiment 83N4, aqueous hydrochloric acid solution
G-C prepared by etching and sodium hydrate aqueous solution etching3N4FT-IR schemes.
Fig. 4 is ZnO, aqueous hydrochloric acid solution etching and sodium hydrate aqueous solution prepared by embodiment 1, embodiment 7 and embodiment 8
Etch the g-C prepared3N4Photocatalytic degradation rhodamine B performance comparison figure.
Specific implementation method
Embodiment 1
Take 1.58 g zinc acetates to be dissolved in 80 mL diethylene glycol (DEG) solvents, add 0.26 mL H2O, which is vigorously stirred, makes it uniformly mix
Close, then above-mentioned solution is warming up at 180 DEG C under violent stirring and reacts 1 h.After system cooling, ethanol washs three times,
100 DEG C are dried to obtain ZnO.Prepared ZnO transmission electron microscope pictures(TEM)As shown in Fig. 1 (b), prepared ZnO nano material
Pattern 300-400 nm of particle diameter and is uniformly dispersed to be regular spherical.The results are shown in Figure 2 by XRD, the diffraction maximum of the ZnO of preparation
It is located at 31.770 °, 34.490 °, 36.420 °, 47.650 °, 56.630 °, 62.890 ° and six direction ZnO of standard respectively
Structure (JCPDS No. 36-1451) fits like a glove.
Embodiment 2
Take 1.58 g zinc acetates to be dissolved in 80 mL diethylene glycol (DEG) solvents, add 0.26 mL H2O, which is vigorously stirred, makes it uniformly mix
Close, then above-mentioned solution is warming up at 190 DEG C under violent stirring and reacts 1 h.After system cooling, ethanol washs three times
It is dried to obtain ZnO for 100 DEG C afterwards.
Embodiment 3
Take 1.58 g zinc acetates to be dissolved in 80 mL diethylene glycol (DEG) solvents, add 0.26 mL H2O, which is vigorously stirred, makes it uniformly mix
Close, then above-mentioned solution is warming up at 200 DEG C under violent stirring and reacts 1 h.After system cooling, ethanol washs three times
It is dried to obtain ZnO for 100 DEG C afterwards.
Embodiment 4
Take 1.58 g zinc acetates to be dissolved in 80 mL diethylene glycol (DEG) solvents, add 0.65 mL H2O, which is vigorously stirred, makes it uniformly mix
Close, then above-mentioned solution is warming up at 180 DEG C under violent stirring and reacts 1 h.After system cooling, ethanol washs three times
It is dried to obtain ZnO for 100 DEG C afterwards.
Embodiment 5
Take 1.58 g zinc acetates to be dissolved in 80 mL diethylene glycol (DEG) solvents, add 1.296 mL H2O, which is vigorously stirred, makes it uniformly mix
Close, then above-mentioned solution is warming up at 180 DEG C under violent stirring and reacts 1 h.After system cooling, ethanol washs three times
It is dried to obtain ZnO for 100 DEG C afterwards.
Embodiment 6
Take 1.58 g zinc acetates to be dissolved in 100 mL diethylene glycol (DEG) solvents, add 0.26 mL H2O, which is vigorously stirred, makes it uniformly mix
Close, then above-mentioned solution is warming up at 180 DEG C under violent stirring and reacts 1 h.After system cooling, ethanol washs three times
It is dried to obtain ZnO for 100 DEG C afterwards.
Embodiment 7
2 g melamine presomas are dissolved in 80 mL deionized waters, are vigorously stirred to obtain settled solution in 80 DEG C, then will be real
Apply 0.75 g ZnO nano particles prepared in example 1 to be scattered in 10 mL ethanol, be slowly added dropwise in above-mentioned solution, ultrasound
Each 1 h is stirred, then white solid powder is obtained by being evaporated under reduced pressure, finally dries it in 100 DEG C of baking ovens.Will be above-mentioned
The white powder grinding of acquisition is uniform, is transferred in crucible with cover, in 550 DEG C of Muffle furnace(2 ℃/min)Handle 3 h.So
It is repeatedly extremely neutral by washing centrifugation afterwards with 4 mol/L hydrochloric acid solutions etching ZnO templates, 12 h, finally obtain faint yellow cage
The g-C of shape pattern3N4Material.Prepared g-C3N4Transmission electron microscope picture(TEM)As shown in Fig. 1 (c), by aqueous hydrochloric acid solution
Etch g-C3N4Hollow ball-shape structure is presented, and further by the way that shown in XRD diagram 2, the characteristic peak of ZnO all disappears, and with leading to
The g-C of Chang Fangfa synthesis3N4Go out peak position 27.4o, 13.1o fits like a glove.The interlayer that 27.4o belongs to graphite phase structure spreads out
Peak is penetrated, weakening, which occurs, in peak intensity illustrates that crystallinity is subject to a degree of influence to cause crystallinity to decline in processing procedure.
13.1o belongs to the diffraction maximum in 100 face of repetitive unit in face, and peak intensity occurs weakening the surface C N material structure degrees of order under
Drop.And through a step by FT-IR spectral characterizations, as shown in figure 3, going out the g-C that peak position is synthesized with usual method3N4Unanimously, into
The explanation of one step is successfully prepared for g-C3N4Caged material.
Embodiment 8
4 g melamine presomas are dissolved in 100 mL deionized waters, are vigorously stirred to obtain settled solution in 80 DEG C, then will
0.75 g ZnO nano particles are scattered in 10 mL ethanol in embodiment 1, are slowly dropped into above-mentioned solution, ultrasonic agitation each 1
H, then obtains white solid powder by being evaporated under reduced pressure, finally dries it in 100 DEG C of baking ovens.By the white of above-mentioned acquisition
Color powder mull is uniform, is then transferred in crucible with cover, 550 DEG C in Muffle furnace(2 ℃/min)Handle 3 h.Then
It is repeatedly extremely neutral by washing centrifugation with 4 mol/L NaOH aqueous solutions etching ZnO templates, 12 h, finally obtain faint yellow cage
The g-C of shape pattern3N4Material.Prepared g-C3N4Transmission electron microscope picture(TEM)As shown in Fig. 1 (d), embodiment 7 is same as above.XRD is such as
Shown in Fig. 2, with aqueous hydrochloric acid solution etching phase ratio, 13.1o characteristic peaks substantially reduce, and illustrate that alkaline etching can be to the degree of order of its structure
Cause significantly to influence.Its crystallinity becomes apparent with respect to what acid etch declined at the same time.FT-IR spectrograms are as shown in Figure 3.
Embodiment 9
8 g melamine presomas are dissolved in 150 mL deionized waters, are vigorously stirred to obtain settled solution in 80 DEG C, then will
0.75 g ZnO nano particles are scattered in 10 mL ethanol in embodiment 1, are slowly added dropwise in above-mentioned solution, ultrasonic agitation each 1
H, then obtains white solid powder by being evaporated under reduced pressure, finally dries it in 100 DEG C of baking ovens.By the white of above-mentioned acquisition
Color powder mull is uniform, is transferred in crucible with cover, in 550 DEG C of Muffle furnace(2 ℃/min)Handle 3 h.Then with 4
Mol/L etches 12 h of ZnO templates with hydrochloric acid solution, by washing centrifugation repeatedly to neutrality, finally obtains faint yellow caged pattern
G-C3N4Material.
Embodiment 10
10 g melamine presomas are dissolved in 200 mL deionized waters, are vigorously stirred to obtain settled solution in 80 DEG C, then will
0.75 g ZnO nano particles are scattered in 10 mL ethanol in embodiment 1, are slowly added dropwise in above-mentioned solution, ultrasonic agitation each 1
H, then obtains white solid powder by being evaporated under reduced pressure, finally dries it in 100 DEG C of baking ovens.By the white of above-mentioned acquisition
Color powder mull is uniform, is transferred in crucible with cover, in 550 DEG C of Muffle furnace(2 ℃/min)Handle 3 h.Then with 4
12 h of mol/L hydrochloric acid solutions etching ZnO templates, it is repeatedly extremely neutral by washing centrifugation, finally obtain faint yellow caged pattern
g-C3N4Material.
Embodiment 11
2 g melamine presomas are dissolved in 80 mL deionized waters, are vigorously stirred to obtain settled solution in 80 DEG C, then will be real
Apply 0.75 g ZnO nano particles in example 1 to be scattered in 10 mL ethanol, be slowly added dropwise in above-mentioned solution, ultrasonic agitation each 1
H, then obtains white solid powder by being evaporated under reduced pressure, finally dries it in 100 DEG C of baking ovens.By the white of above-mentioned acquisition
Color powder mull is uniform, is transferred in crucible with cover, in 500 DEG C of Muffle furnace(2 ℃/min)Handle 3 h.Then with 4
Mol/L etches 12 h of ZnO templates with hydrochloric acid solution, by washing centrifugation repeatedly to neutrality, finally obtains faint yellow caged pattern
G-C3N4Material.
Embodiment 12
2 g melamine presomas are dissolved in 80 mL deionized waters, are vigorously stirred to obtain settled solution in 80 DEG C, then will be real
Apply 0.75 g ZnO nano particles in example 1 to be scattered in 10 mL ethanol, be slowly added dropwise in above-mentioned solution, ultrasonic agitation each 1
H, then obtains white solid powder by being evaporated under reduced pressure, finally dries it in 100 DEG C of baking ovens.By above-mentioned acquisition
White powder grinding it is uniform, be transferred in crucible with cover, in 600 DEG C of Muffle furnace(2 ℃/min)Handle 3 h.Then with 4
Mol/L etches 12 h of ZnO templates with hydrochloric acid solution, by washing centrifugation repeatedly to neutrality, finally obtains faint yellow caged pattern
G-C3N4Material.
Embodiment 13
10 g melamines are taken into crucible with cover, in 550 DEG C of Muffle furnace(2 ℃/min)3 h are handled, obtain usual side
The g-C of method synthesis3N4Material.
Embodiment 14
By the C prepared by embodiment 73N4Caged material is used for photocatalytic degradation rhodamine B (RhB), and experiment condition includes:It is real
Apply the g-C of the preparation of example 133N4Catalyst:0.05 g, g-C prepared by embodiment 73N4Cage catalyst:It is prepared by 0.05 g, embodiment 8
G-C3N4Cage catalyst:0.05 g, RhB concentration:4.5 mg/L temperature:25 DEG C, it is seen that light irradiation power:300 W.
Corresponding 0.05g catalyst is taken respectively in 50 mL beakers, and it is 4.5 mg/L's then to add 50 mL concentration
RhB solution simultaneously stirs 30 minutes to reach adsorption equilibrium in dark place.Then it is placed under visible light device, is passed through circulation
Condensed water, samples 1 time for every 15 minutes(Take 5 mL every time), centrifuged 5 minutes under the rotating speed of 8000 r/min, take supernatant in
Its residual concentration is measured under 553 nm excitation wavelengths.The results are shown in Figure 4, and the degraded to RhB does not almost have ZnO under visible light
There is effect, in the g-C prepared using ZnO as template3N4There is difference in the RhB that degrades in cage, wherein with the g-C after acid etch3N4
Cage is best in the effect of photocatalytic degradation rhodamine B.The g-C that two kinds of different etching methods obtain during 100 min3N4Cage photocatalysis
Rhodamine B degradation efficiency is respectively 60 % and 40 %.
Claims (10)
- A kind of 1. cage structure material g-C3N4Preparation method, it is characterised in that using ZnO as hard template, using melamine before Drive the C of body synthesis nanocage structure3N4Material, and acid solution or alkaline solution are used as etching agent.
- A kind of 2. cage structure material g-C according to claim 13N4Preparation method, it is characterised in that the acidity Solution is hydrochloric acid, and the alkaline solution is sodium hydroxid aqueous solution.
- A kind of 3. cage structure material g-C according to claim 23N4Preparation method, it is characterised in that according to following Step carries out:Melamine presoma is soluble in water, settled solution is obtained in 50 DEG C of -80 DEG C of stirrings, then ZnO nano particle is disperseed In ethanol, it is slowly added dropwise into above-mentioned solution, and is stirred by ultrasonic uniformly, then passes through and be evaporated under reduced pressure acquisition white solid powder; Finally drying in 80 DEG C of -100 DEG C of baking ovens by it;The white powder grinding of above-mentioned acquisition is uniform, then in 500 DEG C of -550 DEG C of 1 h -3 h of roasting;Then with acid molten Liquid or alkaline solution etching ZnO templates, finally obtain the g-C of faint yellow caged pattern3N4Material.
- A kind of 4. cage structure material g-C according to claim 33N4Preparation method, it is characterised in that presoma three Poly cyanamid and the mass ratio of deionized water are 1:25-1:50, it is completely dissolved under the conditions of 50 DEG C -80 DEG C.
- A kind of 5. cage structure material g-C according to claim 13N4Preparation method, it is characterised in that the ZnO moulds Plate agent and melamine mass ratio are 1:1-10:1.
- A kind of 6. cage structure material g-C according to claim 13N4Preparation method, it is characterised in that hydrochloric acid solution Or the concentration of sodium hydrate aqueous solution is 3-5 mol/L.
- A kind of 7. cage structure material g-C according to any of the above-described claim3N4Preparation method, it is characterised in that on Used ZnO templates are stated to prepare using forced hydrolysis method:Zinc acetate is dissolved in diethylene glycol (DEG) solvent, adds water, then will It is warming up under above-mentioned solution stirring under certain temperature and reacts 0.5-1 h;After system is taken out cooling, 80 after being washed three times with ethanol DEG C -100 DEG C are dried to obtain ZnO.
- A kind of 8. cage structure material g-C according to claim 83N4Preparation method, it is characterised in that stepSecond The concentration of sour zinc solution is 0.06-0.2 mol/L.
- A kind of 9. cage structure material g-C according to claim 73N4Preparation method, it is characterised in that H2O and Zn2+ The amount ratio of material be 0-20, reaction temperature is 170-210 DEG C.
- 10. the g-C that any of the above-described claim is prepared3N4Application, it is characterised in that applied to photocatalytic degradation Luo Dan Among bright B.
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