CN108435228A - One kind preparing g-C based on hard template method3N4The technique of nanotube - Google Patents
One kind preparing g-C based on hard template method3N4The technique of nanotube Download PDFInfo
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- CN108435228A CN108435228A CN201810209203.XA CN201810209203A CN108435228A CN 108435228 A CN108435228 A CN 108435228A CN 201810209203 A CN201810209203 A CN 201810209203A CN 108435228 A CN108435228 A CN 108435228A
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- 239000002071 nanotube Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 22
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 11
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 238000001354 calcination Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 150000007974 melamines Chemical class 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 230000000873 masking effect Effects 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002734 clay mineral Substances 0.000 abstract description 3
- 238000013019 agitation Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010792 warming Methods 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
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses one kind preparing g C based on hard template method3N4The technique of nanotube by the high-temperature calcination of galapectite elder generation, then through acid etch, prepares the halloysite nanotubes that surface is rich in pore passage structure；Using melamine as presoma, using halloysite nanotubes as hard mould agent, melamine is vapor-deposited on halloysite nanotubes surface through high temperature thermal polycondensation, obtains galapectite@g C3N4Compound, then the galapectite template in compound is removed to get to g C3N4Nanotube.Hard mould agent used in the present invention is clay mineral galapectite, and rich reserves are easy to get, of low cost, are conducive to industrialized production；The g C of preparation3N4Nanotube specific surface area is high, and photocatalysis performance is good, has broad application prospects.
Description
Technical field
The present invention relates to field of photocatalytic material, more particularly to a kind of hard template method that is based on to prepare g-C3N4The work of nanotube
Skill.
Background technology
With the high speed development of social economy, it is in the urgent need to address that lack of energy and environmental degradation have become the mankind
Problem.Inexhaustible solar energy can be converted to stable chemistry by the light-catalyzed reaction carried out by driving force using sunlight
Can and store, this just needs a series of photochemical catalysts haveing excellent performance, g-C3N4Be exactly one of which efficiently, stablize and not
The visible-light photocatalyst of metallic components is applied to the correlative study of photocatalysis Decomposition aquatic products hydrogen.
Synthesis g-C at present3N4Mode mainly by warming polycondensation cyanamide, dicyandiamide, melamine, urea etc. one
Serial nitrogenous precursor prepares g-C3N4, preparation process is simple, cheap, is expected to realize that the extensive of photocatalysis technology answers
With.But g-C prepared by traditional thermal polycondensation process3N4Specific surface area is low, and light induced electron, hole are easily compound, the transmission of photo-generated carrier
Rate is slow etc., this hinders g-C significantly3N4Application.
In recent years, researcher uses a variety of methods to g-C3N4It is modified, is effectively improved photocatalytic
Can, in general, current main method of modifying has the following：
1) element doping and combined polymerization are modified g-C3N4Photochemical catalyst：Element doping and combined polymerization are to change g-C3N4Electronics
The important means of band structure, in g-C3N4Middle doping a small amount of metal/non-metal element or combined polymerization can effectively improve g-
C3N4Light absorpting ability, and then improve its photocatalysis performance.The doping of metallic element is mainly penetrated by metallic atom
g-C3N4Skeleton structure in, to change g-C3N4Valence band and conduction band structure；And nonmetal doping is mainly using non-
Metallic atom replaces g-C3N4In the atoms such as C, N be modified, change g-C to reach3N4The purpose of electronic band structure.
2)g-C3N4Base composite photocatalyst：g-C3N4It is the polymer that a kind of crystallinity is low, exciton binding energy is high.With it is big
Most polymer semiconductor is the same, its light induced electron, hole are easily compound, causes its photocatalysis quantum efficiency very low, is mesh
The preceding principal element for restricting its photocatalytic activity.By g-C3N4It is compound with other photochemical catalysts, the suction of its light can not only be effectively increased
Receipts ability, it is often more important that can effectively hinder light induced electron, hole it is compound, and then improve photocatalysis performance.Mainly with
Its compound substance has metal salt, metal oxide etc., such as BiVO4, TiO2, ZnO etc..
3) nano modification g-C3N4Photochemical catalyst：For theoretically, single layer g-C3N4Specific surface area up to 2500m2/ g,
And g-C prepared by traditional thermal polycondensation process3N4Specific surface area only have 10m2/ g, this makes g-C3N4It is generated in light-catalyzed reaction
Active site is considerably less, so it is the important means for effectively improving photocatalytic activity to increase its surface area.Main nanosizing changes
Property method has hard template method, soft template method and template-free method.In contrast, hard template method is that current nano modification is the most frequently used
Method.Such as prepare g-C by hard template of SBA-153N4Nanometer rods prepare g-C by hard mould agent of AAO3N4Nanometer rods, with
Nano silicon dioxide is that hard mould agent prepares g-C3N4Hollow ball etc..Hard template method can synthesize the g-C of specific morphology3N4, such as receive
Rice stick structure, nucleocapsid etc. can effectively improve the specific surface area of photochemical catalyst, and then improve photocatalysis performance, be a kind of
Very effective method of modifying.But traditional hard template method synthesis nano g-C3N4The shortcomings that it is equally inevitable.Such as it is used
Template be all mostly it is artificial synthesized, it is expensive, be not suitable for photochemical catalyst extensive preparation.This is just seriously constrained
Photocatalysis technology is popularized, so, the use cost of template is reduced, is very important.
Invention content
In view of this, the embodiment provides a kind of of low cost, operation is simple, and photocatalytic is higher
G-C is prepared based on hard template method3N4The technique of nanotube.
The embodiment provides one kind preparing g-C based on hard template method3N4The technique of nanotube, by galapectite elder generation
High-temperature calcination, then through acid etch, prepare the halloysite nanotubes that surface is rich in pore passage structure；Using melamine as presoma,
Using halloysite nanotubes as hard mould agent, melamine is vapor-deposited on halloysite nanotubes surface, obtains through high temperature thermal polycondensation
Galapectite@g-C3N4Compound, then the galapectite template in compound is removed to get to g-C3N4Nanotube.
Further, include the following steps：
S1. by galapectite at 850 DEG C calcining and activating；
S2. galapectite is placed in hydrochloric acid, is stirred to react at 80 DEG C, obtains suspension；
S3. it centrifuges, the solid matter in suspension is separated；
S4. it is neutrality by solid matter centrifuge washing to supernatant liquor, then solid matter is dried and is rich in get to surface
The halloysite nanotubes of pore passage structure；
S5., halloysite nanotubes are placed on to the top of a round platform, round platform is placed in a crucible, is disperseed in crucible
Melamine, and melamine is in the bottom periphery of round platform, then calcining 4h is sealed, natural cooling takes out round platform, the top of round platform
To pass through the obtained galapectite@g-C that are vapor-deposited3N4Compound；
S6. by galapectite@g-C3N4Compound and hydrofluoric acid mixing, stirring at normal temperature react 10h, and solids is isolated in centrifugation
Matter；
S7. it is neutrality by solid matter centrifuge washing to supernatant liquor, freeze-drying is to get to g-C3N4Nanotube.
Further, in the step S1, galapectite is calcined in Muffle furnace, soaking time 4h, heating rate be 10 DEG C/
min。
Further, in the step S2, quality proportioning is the hydrochloric acid that 5g galapectites correspond to a concentration of 5mol/L of 100g.
Further, in the step S4, solid matter is dry at 110 DEG C.
Further, in the step S5,0.5~1g halloysite nanotubes is placed on to the top of a round platform, round platform is put
It sets in a 300ml crucibles, 5~10g melamines is disperseed in crucible, with two layers of masking foil by sealed crucible, in Muffle furnace
Middle calcining, calcination temperature are 520~580 DEG C, 15 DEG C/min of heating rate.
Further, in the step S6, the mass concentration of hydrofluoric acid is 15%.
Compared with prior art, the beneficial effects of the present invention are：
1, hard mould agent used in this technique is clay mineral galapectite, and rich reserves are easy to get, of low cost, favorably
In industrialized production；
2, g-C prepared by this technique3N4Nanotube is compared to body phase g-C3N4With higher specific surface area, visible light
Water hydrogen-producing speed is catalytically decomposed up to 633 μm of olg-1·h-1, about body phase g-C3N414 times, be that a kind of light of function admirable is urged
Agent has broad application prospects.
Description of the drawings
Fig. 1 is of the invention a kind of based on hard template method preparation g-C3N4One flow chart of nanotube technology.
Fig. 2 is g-C made from one embodiment of the invention3N4Nanotube and body phase g-C3N4Scanning electron microscope (SEM) photograph and transmission electron microscope
Figure comparison diagram, a are body phase g-C3N4Scanning electron microscope (SEM) photograph, b be body phase g-C3N4Transmission electron microscope picture, c g-C3N4Nanotube
Scanning electron microscope (SEM) photograph, d g-C3N4The transmission electron microscope picture of nanotube.
Fig. 3 is g-C made from one embodiment of the invention3N4Nanotube and body phase g-C3N4Nitrogen adsorption-desorption isotherm
With the pore-size distribution comparison diagram with BJH model analysis, a is nitrogen adsorption-desorption isotherm comparison diagram, and b is pore-size distribution pair
Than figure.
Fig. 4 is g-C made from one embodiment of the invention3N4Nanotube and body phase g-C3N4Visible light catalytic hydrogen-producing speed
Comparison diagram, a are visible light catalytic hydrogen-producing speed comparison diagram, and b is that visible light catalytic produces stabilized hydrogen comparison diagram.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
G-C is prepared based on hard template method referring to FIG. 1, the embodiment provides one kind3N4The technique of nanotube,
By the high-temperature calcination of galapectite elder generation, then through acid etch, prepare the halloysite nanotubes that surface is rich in pore passage structure；With melamine
For presoma, using halloysite nanotubes as hard mould agent, melamine is vapor-deposited through high temperature thermal polycondensation in halloysite nanotubes
Surface obtains galapectite@g-C3N4Compound, then go in compound except galapectite template is to get to g-C3N4Nanotube.
Specifically include the following steps：
S1. by galapectite, calcining and activating, soaking time 4h, heating rate are 10 DEG C/min at 850 DEG C in Muffle furnace；
Purpose is that galapectite is made to be changed into metakaolin, may be carried out according to the galapectite place of production, the different of type in practical operation
Optimization appropriate；
S2. galapectite being placed in hydrochloric acid, quality proportioning is that 5g galapectites correspond to the hydrochloric acid of a concentration of 5mol/L of 100g, 80
It is stirred to react at DEG C, obtains suspension；The essence of hydrochloric acid activation is to be dissolved alumina composition therein by acid etch, oxidation
Silicon ingredient retains in situ, makes to generate nano pore on its tube wall, increases its specific surface area, be conducive to halloysite nanotubes and g-
C3N4Contact；
S3. it centrifuges, the solid matter in suspension is separated；
S4. be neutrality by solid matter centrifuge washing to supernatant liquor, then will be dried at 110 DEG C of solid matter to get to
Surface is rich in the halloysite nanotubes of pore passage structure；
S5., 0.5~1g halloysite nanotubes are placed on to the top of a round platform, round platform is placed in a 300ml crucibles,
Disperse 5~10g melamines in crucible, and melamine is in the bottom periphery of round platform, then seal calcining, preferably with two layers of tin
Sealed crucible is calcined 4h, 15 DEG C/min of heating rate by foil paper in Muffle furnace at 520~580 DEG C, natural cooling takes out circle
The top of platform, round platform is by the obtained galapectite@g-C that are vapor-deposited3N4Compound；
Thermal polycondensation is initially formed intermediate melem to melamine at high temperature, and galapectite table is deposited in a manner of gas
Face, then form g-C in the further thermal polycondensation in galapectite surface3N4To get to galapectite@g-C3N4Compound.
S6. by galapectite@g-C3N4Compound and hydrofluoric acid mixing, the mass concentration of hydrofluoric acid is 15%, by 1g SiO2
Corresponding 50g hydrofluoric acid calculates, and stirring at normal temperature reacts 10h, by the remaining framework ingredient SiO of halloysite nanotubes2It gets rid of, from
The heart isolates solid matter；
S7. it is neutrality by solid matter centrifuge washing to supernatant liquor, freeze-drying is to get to g-C3N4Nanotube.
A, the main chemical compositions of galapectite original sample are SiO2And Al2O3, constitution water is sloughed at 700 DEG C or less, at 850 DEG C
It is changed into metakaolin；
B, the galapectite after calcining is by salt acid etch, during acid etch, calcines in halloysite nanotubes wall wall
Al2O3Component is selectively dissolved out, and SiO2Then retain with component in situ, to constitute micropore in nanometer tube wall
Or mesopore orbit, make it have higher specific surface area；
C, g-C is formed in thermal polycondensation3N4During, presoma can form intermediate first, and diffusional deposition is received to galapectite
Nanotube surface, when temperature rises to 520~580 DEG C, intermediate is in the further thermal polycondensation in galapectite surface at g-C3N4, natural
That obtained after cooling is exactly galapectite@g-C3N4Compound；
D, hydrofluoric acid and galapectite@g-C3N4During compound reacts, hydrofluoric acid can be by the main component in galapectite
SiO2It etches away, without to g-C3N4It damages, then by centrifuging, removes the galapectite etched away, you can obtain
g-C3N4Nanotube.
The method have the characteristics that used hard mould agent is clay mineral galapectite, rich reserves are easy to get, significantly
Reduce the manufacturing cost of photochemical catalyst.
G-C produced by the present invention3N4Nanotube is compared to body phase g-C3N4With higher specific surface area, it is seen that photocatalysis
Hydrogen-producing speed is up to 633 μm of olg-1·h-1, with body phase g-C3N4It compares, Photocatalyzed Hydrogen Production rate improves 14 times.System of the present invention
The g-C obtained3N4Nanotube is compared to body phase g-C3N4Performance comparison as shown in figs 2-4, from figure 2 it can be seen that g-C3N4
The caliber of nanotube is about 70nm, and pattern shows not enough rule, the broken of part occurs, this is firstly because galapectite table
Face g-C3N4Deposition thickness is uneven, followed by g-C during removing galapectite template3N4The structure of nanotube occurs
Caused by caving in.Fig. 3 is g-C3N4Nanotube and body phase g-C3N4Nitrogen adsorption-desorption curve and graph of pore diameter distribution.It is computed table
It is bright, g-C3N4The specific surface area of nanotube has reached 85.50m2/ g, compared with body phase g-C3N4Have greatly improved.G-C in Fig. 43N4
The visible light catalytic hydrogen-producing speed of nanotube is up to 633 μm of olg-1·h-1, it is body phase g-C3N414 times.g-C3N4Nanotube exists
It is maintained to good photocatalytic activity after the circular response of 12h, there is higher stability.
Embodiment 1
G-C is prepared by hard mould agent of galapectite3N4Nanotube, it includes the following steps：
(1) calcining and activating：First galapectite is placed at 850 DEG C and carries out high-temperature calcination, heating rate is set as 10 DEG C/min,
Soaking time is set as 4h；
(2) acid activation：Galapectite after calcining is activated with the hydrochloric acid of 5mol/L, quality proportioning is per 5g galapectites
Corresponding 100g hydrochloric acid.By mixture, magnetic agitation reacts 6h under conditions of 80 DEG C, and centrifuge washing is to neutrality later, then by solid
Substance 110 DEG C of dryings in an oven；
(3) galapectite@g-C are prepared3N4Compound：The processed galapectite of 0.5g acid is placed at the top of round platform again, is put
It is scattered in crucible in 300ml crucibles center, then by 5g melamines, is sealed against using two layers of masking foil, places it in horse
Not calcine 4h in stove at 520 DEG C, 15 DEG C/min of heating rate takes out after natural cooling；
(4) by prepared galapectite@g-C3N4Compound is placed in the hydrofluoric acid solution that mass fraction is 15%, according to
Galapectite@g-C3N4Per 1g SiO in compound2Corresponding 50g hydrofluoric acid calculates, and magnetic agitation reacts 10h under room temperature, carries out later
Centrifugation, it is neutrality, freeze-drying that deionized water, which is washed to supernatant liquor,.
Embodiment 2
G-C is prepared by hard mould agent of galapectite3N4Nanotube, it includes the following steps：
(1) calcining and activating：First galapectite is placed at 850 DEG C and carries out high-temperature calcination, heating rate is set as 10 DEG C/min,
Soaking time is set as 4h；
(2) acid processing：Galapectite after calcining is activated with the hydrochloric acid of 5mol/L, quality proportioning is per 5g galapectites
Corresponding 100g hydrochloric acid.By mixture, magnetic agitation reacts 6h under conditions of 80 DEG C, and centrifuge washing is to neutrality later, then will precipitate
It is dry at 110 DEG C in an oven；
(3) galapectite@g-C are prepared3N4Compound：The processed galapectite of 0.7g acid is placed at the top of round platform again, is put
It is scattered in crucible in 300ml crucibles center, then by 10g melamines, is sealed against using two layers of masking foil, places it in horse
Not calcine 4h in stove at 560 DEG C, 15 DEG C/min of heating rate takes out after natural cooling；
(4) by prepared galapectite@g-C3N4Compound is placed in the hydrofluoric acid solution that mass fraction is 15%, according to
Galapectite/g-C3N4Per 1g SiO in compound2Corresponding 50g hydrofluoric acid calculates, and magnetic agitation reacts 10h under room temperature, carries out later
Centrifugation, it is neutrality, freeze-drying that deionized water, which is washed to supernatant liquor,.
Embodiment 3
G-C is prepared by hard mould agent of galapectite3N4Nanotube, it includes the following steps：
(1) calcining and activating：First galapectite is placed at 850 DEG C and carries out high-temperature calcination, heating rate is set as 10 DEG C/min,
Soaking time is set as 4h；
(2) acid processing：Galapectite after calcining is activated with the hydrochloric acid of 5mol/L, quality proportioning is per 5g galapectites
Corresponding 100g hydrochloric acid.By mixture, magnetic agitation reacts 6h under conditions of 80 DEG C, during centrifuge washing is to supernatant liquor later
Property, then will the precipitation drying at 110 DEG C in an oven；
(3) galapectite@g-C are prepared3N4Compound：The processed galapectite of 1g acid is placed at the top of round platform again, is placed it in
300ml crucibles center, then 7g melamines are scattered in crucible, it is sealed against using two layers of masking foil, places it in Muffle
Calcine 4h in stove at 580 DEG C, 15 DEG C/min of heating rate takes out after natural cooling；
(4) by prepared galapectite@g-C3N4Compound is placed in the hydrofluoric acid solution that mass fraction is 15%, according to
Galapectite/g-C3N4Per 1g SiO in compound2Corresponding 50g hydrofluoric acid calculates, and magnetic agitation reacts 10h under room temperature, carries out later
Centrifugation, it is neutrality, freeze-drying that deionized water, which is washed to supernatant liquor,.
Embodiment 4
G-C is prepared by hard mould agent of galapectite3N4Nanotube, it includes the following steps：
(1) calcining and activating：First galapectite is placed at 850 DEG C and carries out high-temperature calcination, heating rate is set as 10 DEG C/min,
Soaking time is set as 4h；
(2) acid processing：Galapectite after calcining is activated with the hydrochloric acid of 5mol/L, quality proportioning is per 5g galapectites
Corresponding 100g hydrochloric acid.By mixture, magnetic agitation reacts 6h under conditions of 80 DEG C, during centrifuge washing is to supernatant liquor later
Property, then will the precipitation drying at 110 DEG C in an oven；
(3) galapectite@g-C are prepared3N4Compound：The processed galapectite of 1g acid is placed at the top of round platform again, is placed it in
300ml crucibles center, then 9g melamines are scattered in crucible, it is sealed against using two layers of masking foil, places it in Muffle
Calcine 4h in stove at 550 DEG C, 15 DEG C/min of heating rate takes out after natural cooling；
(4) by prepared galapectite@g-C3N4Compound is placed in the hydrofluoric acid solution that mass fraction is 15%, according to
Galapectite-g-C3N4Per 1g SiO in compound2Corresponding 50g hydrofluoric acid calculates, and magnetic agitation reacts 10h under room temperature, carries out later
Centrifugation, it is neutrality, freeze-drying that deionized water, which is washed to supernatant liquor,.
Embodiment 5
G-C is prepared by hard mould agent of galapectite3N4Nanotube, it includes the following steps：
(1) calcining and activating：First galapectite is placed at 850 DEG C and carries out high-temperature calcination, heating rate is set as 10 DEG C/min,
Soaking time is set as 4h；
(2) acid processing：Galapectite after calcining is activated with the hydrochloric acid of 5mol/L, quality proportioning is per 5g galapectites
Corresponding 100g hydrochloric acid.By mixture, magnetic agitation reacts 6h under conditions of 80 DEG C, during centrifuge washing is to supernatant liquor later
Property, then will the precipitation drying at 110 DEG C in an oven；
(3) galapectite@g-C are prepared3N4Compound：The processed galapectite of 0.7g acid is placed at the top of round platform again, is put
It is scattered in crucible bottom in 300ml crucibles center, then by 8g melamines, is sealed against, is placed it in using two layers of masking foil
Calcine 4h in Muffle furnace at 570 DEG C, 15 DEG C/min of heating rate takes out after natural cooling；
(4) by prepared galapectite@g-C3N4Compound is placed in the hydrofluoric acid solution that mass fraction is 15%, according to
Galapectite-g-C3N4Per 1g SiO in compound2Corresponding 50g hydrofluoric acid calculates, and magnetic agitation reacts 10h under room temperature, carries out later
Centrifugation, it is neutrality, freeze-drying that deionized water, which is washed to supernatant liquor,.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (7)
1. one kind preparing g-C based on hard template method3N4The technique of nanotube, which is characterized in that by the high-temperature calcination of galapectite elder generation, then
Through acid etch, the halloysite nanotubes that surface is rich in pore passage structure are prepared；Using melamine as presoma, with galapectite nanometer
Pipe is hard mould agent, and melamine is vapor-deposited on halloysite nanotubes surface through high temperature thermal polycondensation, obtains galapectite@g-C3N4
Compound, then the galapectite template in compound is removed to get to g-C3N4Nanotube.
2. according to claim 1 prepare g-C based on hard template method3N4The technique of nanotube, which is characterized in that including with
Lower step：
S1. by galapectite at 850 DEG C calcining and activating；
S2. galapectite is placed in hydrochloric acid, is stirred to react at 80 DEG C, obtains suspension；
S3. it centrifuges, the solid matter in suspension is separated；
S4. it is neutrality by solid matter centrifuge washing to supernatant liquor, then solid matter is dried and is rich in duct to get to surface
The halloysite nanotubes of structure；
S5., halloysite nanotubes are placed on to the top of a round platform, round platform is placed in a crucible, trimerization is disperseed in crucible
Cyanamide, and melamine is in the bottom periphery of round platform, then calcining 4h is sealed, natural cooling takes out round platform, and the top of round platform is logical
Cross the galapectite@g-C that vapor deposition obtains3N4Compound；
S6. by galapectite@g-C3N4Compound and hydrofluoric acid mixing, stirring at normal temperature react 10h, and solid matter is isolated in centrifugation；
S7. it is neutrality by solid matter centrifuge washing to supernatant liquor, freeze-drying is to get to g-C3N4Nanotube.
3. according to claim 2 prepare g-C based on hard template method3N4The technique of nanotube, which is characterized in that the step
In rapid S1, galapectite is calcined in Muffle furnace, soaking time 4h, and heating rate is 10 DEG C/min.
4. according to claim 2 prepare g-C based on hard template method3N4The technique of nanotube, which is characterized in that the step
In rapid S2, quality proportioning is the hydrochloric acid that 5g galapectites correspond to a concentration of 5mol/L of 100g.
5. according to claim 2 prepare g-C based on hard template method3N4The technique of nanotube, which is characterized in that the step
In rapid S4, solid matter is dry at 110 DEG C.
6. according to claim 2 prepare g-C based on hard template method3N4The technique of nanotube, which is characterized in that the step
In rapid S5,0.5~1g halloysite nanotubes are placed on to the top of a round platform, round platform are placed in a 300ml crucibles, in earthenware
In crucible disperse 5~10g melamines calcined in Muffle furnace with two layers of masking foil by sealed crucible, calcination temperature be 520~
580 DEG C, 15 DEG C/min of heating rate.
7. according to claim 2 prepare g-C based on hard template method3N4The technique of nanotube, which is characterized in that the step
In rapid S6, the mass concentration of hydrofluoric acid is 15%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772419A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | The preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material is constructed in confinement space |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102398902A (en) * | 2011-07-21 | 2012-04-04 | 中国地质大学（武汉） | Method for preparing carbon nano material by using natural endellite as formwork |
| CN103657699A (en) * | 2013-12-12 | 2014-03-26 | 上海师范大学 | G-C3N4 quantum dot modified titanium oxide nanotube catalyst as well as preparation method and application thereof |
| CN105236364A (en) * | 2015-08-27 | 2016-01-13 | 常州大学 | Preparation method of tubular carbon nitride |
| CN105664848A (en) * | 2016-01-14 | 2016-06-15 | 江苏大学 | Preparation method of lignin hierarchical porous carbon material with endellite as template |
| CN105692627A (en) * | 2016-01-18 | 2016-06-22 | 中国地质大学（武汉） | Method for preparing mesoporous silica material from kaolin through template-free method |
| CN107694590A (en) * | 2017-08-30 | 2018-02-16 | 江苏大学 | A kind of g C3N4‑TiO2The preparation and its application of/HNTs composite photo-catalysts |
-
2018
- 2018-03-14 CN CN201810209203.XA patent/CN108435228A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102398902A (en) * | 2011-07-21 | 2012-04-04 | 中国地质大学（武汉） | Method for preparing carbon nano material by using natural endellite as formwork |
| CN103657699A (en) * | 2013-12-12 | 2014-03-26 | 上海师范大学 | G-C3N4 quantum dot modified titanium oxide nanotube catalyst as well as preparation method and application thereof |
| CN105236364A (en) * | 2015-08-27 | 2016-01-13 | 常州大学 | Preparation method of tubular carbon nitride |
| CN105664848A (en) * | 2016-01-14 | 2016-06-15 | 江苏大学 | Preparation method of lignin hierarchical porous carbon material with endellite as template |
| CN105692627A (en) * | 2016-01-18 | 2016-06-22 | 中国地质大学（武汉） | Method for preparing mesoporous silica material from kaolin through template-free method |
| CN107694590A (en) * | 2017-08-30 | 2018-02-16 | 江苏大学 | A kind of g C3N4‑TiO2The preparation and its application of/HNTs composite photo-catalysts |
Non-Patent Citations (1)
| Title |
|---|
| ZHU SHU ET AL.: ""Nanoporous g-C3N4 nanosheets: Facile synthesis and excellent visible-light photocatalytic H2 evolution performance"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (14)
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|---|---|---|---|---|
| CN109772419B (en) * | 2019-03-11 | 2021-12-28 | 辽宁石油化工大学 | Preparation method for constructing carbon nitride-based ultrathin nanosheet composite material in confined space |
| CN109772419A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | The preparation method for nitrogenizing carbon-based ultrathin nanometer piece composite material is constructed in confinement space |
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| CN111229287B (en) * | 2020-03-25 | 2022-10-21 | 吉林师范大学 | Carbon fiber cloth load tubular g-C 3 N 4 Photocatalytic material and method for producing same |
| CN111229287A (en) * | 2020-03-25 | 2020-06-05 | 吉林师范大学 | Carbon fiber cloth load tubular g-C3N4Photocatalytic material and preparation method thereof |
| CN114763258A (en) * | 2021-01-12 | 2022-07-19 | 上饶师范学院 | Method for preparing carbon tri-nitrogen four-nanosheet powder by water-soluble salt template method |
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