CN108147380A - A kind of preparation method of honeycomb carbonitride - Google Patents
A kind of preparation method of honeycomb carbonitride Download PDFInfo
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- CN108147380A CN108147380A CN201810013728.6A CN201810013728A CN108147380A CN 108147380 A CN108147380 A CN 108147380A CN 201810013728 A CN201810013728 A CN 201810013728A CN 108147380 A CN108147380 A CN 108147380A
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- sepiolite
- carbon nitride
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- carbonitride
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 46
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 44
- 239000004113 Sepiolite Substances 0.000 claims abstract description 43
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001690 polydopamine Polymers 0.000 claims abstract description 29
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 19
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- 239000007853 buffer solution Substances 0.000 claims description 10
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002641 lithium Chemical class 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 238000006303 photolysis reaction Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 241000264877 Hippospongia communis Species 0.000 description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000010439 graphite Substances 0.000 description 13
- 229910002804 graphite Inorganic materials 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 206010013786 Dry skin Diseases 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 150000007974 melamines Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001912 cyanamides Chemical class 0.000 description 2
- -1 dicyandiamide melamines Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- B01J35/39—
-
- B01J35/56—
-
- B01J35/615—
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods for the honeycomb carbonitride for having and being bonded hollow cavity structure, it is characterised in that preparation process includes the following steps：A) sepiolite acid is handled；B) sepiolite poly-dopamine coating modification；C) sepiolite of poly-dopamine coating modification is uniformly mixed with carbon nitride precursor, then high-temperature roasting；D) removing template is removed, obtains honeycomb carbonitride.Using sepiolite cheap and easy to get as hard template, poly-dopamine effectively simplifies the preparation process of bigger serface carbonitride, reduces its production cost the present invention as binding agent.What is more important has unique cavity structure and larger specific surface area using the honeycomb carbonitride that the method for the present invention is prepared, has excellent visible light photocatalysis active, can be widely applied to the fields such as photolysis water hydrogen, photocatalytic pollutant degradation.
Description
Technical field
The present invention relates to a kind of preparation methods of honeycomb carbon nitride material, belong to field of material preparation.
Background technology
Photocatalitic Technique of Semiconductor is the excitation generation photoproduction electricity under the irradiation of light using the special electronic structure of semiconductor
Son-hole pair, in semiconductor surface initiated oxidation reduction reaction, so that solar energy is converted into chemistry under mild conditions
Can, it can be applied to photo-catalyst, illumination degrading pollutant, CO2The fields such as reduction and photolysis water hydrogen gas and oxygen.
Graphite phase carbon nitride is a kind of organic semiconductor catalysis material, it is free of metallic element, has raw material sources
Extensively, simple, cheap, energy gap narrow (about 2.7eV), the visible light-responded advantages such as good are prepared.But using conventional heat
Smaller (the 10-20m of the usual specific surface area of graphite phase carbon nitride prepared by solution method2g-1).Specific surface area is small to cause its surface to be reacted
Active sites are less, are unfavorable for the separation and transfer of photo-generated carrier, therefore, graphite phase carbon nitride catalysis material activity compared with
It is low.
The specific surface area for improving graphite phase carbon nitride is one of effective ways for improving its photocatalytic activity, wherein passing through mould
It is the common method for improving graphite phase carbon nitride specific surface area that plate method, which prepares hollow structure,.At present, hollow structure graphite-phase is prepared
The template that carbonitride uses mainly has：SiO2Nanosphere (patent：105217584A)、SBA-15(DOI:10.1021/
Cm902130z), mesoporous silicon oxide (DOI:10.1038/ncomms14430) etc..These methods, though specific surface area can be made
Larger graphite phase carbon nitride catalysis material, but there is also some shortcomings simultaneously：(1) template higher price causes prepared
Graphite phase carbon nitride catalysis material cost it is higher；(2) graphite phase carbon nitride presoma for example melamine, urea, cyanamide,
Dicyandiamide etc., and the combination of template are unsatisfactory.The graphite phase carbon nitride of bigger serface is made, generally requires to carry out template
Complicated modification.This not only so that the preparation process of graphite phase carbon nitride is complicated, while also further increases and be produced into
This.Therefore, how using cheap material, the graphite-phase that bigger serface is prepared by easy method nitrogenizes as template
Carbon has great significance for its practical application.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to a kind of honeycomb carbonitride of large specific surface area is provided
Preparation method.
A kind of preparation method of honeycomb carbon nitride material, it is characterised in that preparation process includes the following steps：
A) sepiolite acid is handled；
B) sepiolite poly-dopamine coating modification；
C) poly-dopamine coating modification sepiolite is uniformly mixed with carbon nitride precursor, then high-temperature roasting；
D) removing template is removed, obtains honeycomb carbonitride.
The honeycomb carbon nitride material has the hollow cavity structure of bonding.The sepiolite acid processing is by sepiolite
With hydrochloric acid, nitric acid reaction, impurity and increase pore volume are removed；The sepiolite poly-dopamine coating modification is that treated by acid
Sepiolite is reacted with Dopamine hydrochloride in buffer solution, generates poly-dopamine modified lithium sepiolite；It is described removing template is gone to be will be poly-
Dopamine coating modification sepiolite is reacted with carbon nitride precursor high-temperature roasting product with etching agent.The pH value of the buffer solution
It is 8~9；A concentration of 1~5mg/ml of the Dopamine hydrochloride.The etching agent is any of hydrofluoric acid or ammonium fluoride.Institute
It states carbon nitride precursor and refers to melamine, urea, cyanamide, dicyandiamide any or two kinds or more of mixture.It is poly- more
Bar amine coating modification sepiolite and the mass ratio of carbon nitride precursor are 1~10:1.The high-temperature roasting be in air atmosphere,
Calcination temperature is 500~600 DEG C, and roasting time is 1~5 hour.
The present invention has substantive distinguishing features and marked improvement：1) present invention prepares Large ratio surface using sepiolite as template
Product graphite phase carbon nitride material has many advantages, such as that template is cheap, large specific surface area.Sepiolite is a kind of with layer chain knot
The clay mineral of structure, inside are extremely cheap there are abundant hole.It 2), can be significantly using sepiolite as template
Reduce the production cost of hollow graphite phase carbon nitride；The present invention is anti-with the oxygen in air in buffer solution by Dopamine hydrochloride
Should, generation poly-dopamine clad is not only easy to operate, while also template can be made to be well combined with graphite phase carbon nitride presoma,
The advantages such as prepared honeycomb carbonitride large specific surface area.In the template of identical mass ratio：Under conditions of presoma, using poly-
The 5 of the specific surface area (embodiment 3) about untreated (comparative example 2) of prepared honeycomb carbonitride after dopamine processing
There is excellent Driven by Solar Energy photocatalytic activity, test knot using honeycomb carbonitride made from the method for the invention again)
Fruit shows that the carbonitride hydrogen-producing speed for preparing of the present invention is up to 1061.87umolg in the case where visible ray (λ >=400nm) irradiates-1·h-1Body phase carbon nitride (151.24umolg prepared by (embodiment 3), about comparative example 1-1·h-1) 7 times.
Description of the drawings
Fig. 1 is the transmission electron microscope figure (TEM) of body phase carbon nitride that comparative example 1 is prepared；
Fig. 2 is honeycomb carbonitride transmission electron microscope figure (TEM) prepared by embodiment 3；
Fig. 3 is honeycomb carbonitride (TEM) prepared by embodiment 4；
Fig. 4 is honeycomb carbonitride transmission electron microscope figure (TEM) prepared by embodiment 5；
Fig. 5 is the N of carbonitride made from comparative example 1,2 and embodiment 32Adsorption-desorption curve graph, illustration are made for example 3
The graph of pore diameter distribution of standby honeycomb carbonitride；
Under the body phase carbon nitride visible ray that Fig. 6 is honeycomb carbonitride prepared by embodiment 3 and prepared by comparative example 1,2 (λ >=
400nm) photocatalytic water H2-producing capacity figure.
Specific embodiment
The technical solution of invention is further described below by way of specific embodiment.
The processing of sepiolite acid can refer in the following manner progress, changes sour processing procedure and is not construed as limiting the invention.
By 100g sepiolites and 1000ml 6mo l/L hydrochloric acid or nitric acid reaction 5h, then it is filtered, washed, dries.
Embodiment 1：
(1) poly-dopamine coating modification Hai Pao is prepared
Weigh 10g acid processing sepiolite ultrasonic disperse 100ml pH=8 H3BO3In-NaOH buffer solutions, add in
The Dopamine hydrochloride of 100mg, oxidation polymerization 12h, centrifugation washing is multiple, 60 DEG C of dryings.
(2) honeycomb carbonitride is prepared
Weigh 5g poly-dopamine coating modifications sepiolite, 5g cyanamides are placed in mortar, after being fully ground, be placed in tube furnace
Under middle air atmosphere, 500 DEG C are warming up to 2 DEG C/min, constant temperature 5h after natural cooling, obtains pale yellow powder.It will heat treatment
The HF aqueous solutions that obtained pale yellow powder mass fraction is 5% etch, and remove sepiolite template, and wash extra HF, and 60
DEG C drying, you can obtain honeycomb carbonitride.
Embodiment 2：
(1) poly-dopamine coating modification Hai Pao is prepared
Weigh 10g acid processing sepiolite ultrasonic disperse 100ml pH=8.5 H3BO3In-NaOH buffer solutions, add in
The Dopamine hydrochloride of 100mg, oxidation polymerization 12h, centrifugation washing is multiple, 60 DEG C of dryings.
(2) honeycomb carbonitride is prepared
Weigh 5g poly-dopamine coating modifications sepiolite respectively, 0.5g melamines are placed in mortar, after being fully ground, put
In tube furnace under air atmosphere, 600 DEG C are warming up to 2 DEG C/min, constant temperature 1h after natural cooling, obtains pale yellow powder.
The HF aqueous solutions that the pale yellow powder mass fraction being thermally treated resulting in is 5% are etched, remove sepiolite template, and wash more
Remaining HF, 60 DEG C of dryings, you can obtain honeycomb carbonitride.
Embodiment 3：
(1) poly-dopamine coating modification Hai Pao is prepared
Weigh 10g acid processing sepiolite ultrasonic disperse 100ml pH=9 H3BO3In-NaOH buffer solutions, add in
The Dopamine hydrochloride of 500mg, oxidation polymerization 12h, centrifugation washing is multiple, 60 DEG C of dryings.
(2) honeycomb carbonitride is prepared
Weigh 5g poly-dopamine coating modifications sepiolite respectively, 2.5g melamines are placed in mortar, after being fully ground, put
In tube furnace under air atmosphere, 550 DEG C are warming up to 2 DEG C/min, constant temperature 2h after natural cooling, obtains pale yellow powder.
The HF aqueous solutions that the pale yellow powder mass fraction being thermally treated resulting in is 5% are etched, remove sepiolite template, and wash more
Remaining HF, 60 DEG C of dryings, you can obtain honeycomb carbonitride, specific area area is about 389.2m2·g-1。
Embodiment 4：
(1) poly-dopamine coating modification Hai Pao is prepared
Weigh 10g acid processing sepiolite ultrasonic disperse 100ml pH=8.5 H3BO3In-NaOH buffer solutions, add in
The Dopamine hydrochloride of 100mg, oxidation polymerization 12h, centrifugation washing is multiple, 60 DEG C of dryings.
(2) honeycomb carbonitride is prepared
5g poly-dopamine coating modifications sepiolite, 1.25g urea and 1.25g melamines is weighed respectively to be placed in mortar,
It after being fully ground, is placed in tube furnace under air atmosphere, is warming up to 600 DEG C with 2 DEG C/min, constant temperature 1h after natural cooling, is obtained
To pale yellow powder.5% NH for being with mass fraction by the pale yellow powder being thermally treated resulting in4F aqueous solutions etch, removal sea
Afrodite template, and wash extra NH4F, 60 DEG C of dryings, you can obtain honeycomb carbonitride.
Embodiment 5：
(1) poly-dopamine coating modification Hai Pao is prepared
Weigh 10g acid processing sepiolite ultrasonic disperse 100ml pH=8.5 H3BO3In-NaOH buffer solutions, add in
The Dopamine hydrochloride of 100mg, oxidation polymerization 12h, centrifugation washing is multiple, 60 DEG C of dryings.
(2) honeycomb carbonitride is prepared
5g poly-dopamine coating modifications sepiolite, 2.5g cyanamides and 2.5g dicyandiamide melamines is weighed respectively to be placed in and grind
It in alms bowl, after being fully ground, is placed in tube furnace under air atmosphere, is warming up to 550 DEG C with 2 DEG C/min, constant temperature 2h treats natural cooling
Afterwards, pale yellow powder is obtained.By the NH that the pale yellow powder mass fraction being thermally treated resulting in is 5%4F aqueous solutions etch, and go
Except sepiolite template, and wash extra NH4F, 60 DEG C of dryings, you can obtain honeycomb carbonitride.
Comparative example 1：
2.5g melamines are weighed, is placed in tube furnace under air atmosphere and is warming up to the heating rate of 2 DEG C/min to 550
DEG C, constant temperature 2h after natural cooling, obtains body phase carbon nitride (bulk g-C3N4), specific area area is about 19.14m2·g-1。
Comparative example 2：
5g acid treated sepiolites and 2.5g melamines are weighed, after grinding uniformly, is placed under tube furnace air atmosphere,
Heating rate is warming up to 550 DEG C for 2 DEG C/min, and constant temperature 2h after natural cooling, obtains pale yellow powder.It will be thermally treated resulting in
Pale yellow powder mass fraction be 5% HF aqueous solutions etch, remove sepiolite template, and wash extra HF, 60 DEG C are dry
It is dry, you can to obtain the honeycomb carbonitride without poly-dopamine coating modification, specific area area is about 78.14m2·g-1。
Fig. 1 is the transmission electron microscope figure (TEM) of body phase carbon nitride prepared by comparative example 1.From figure as it can be seen that by melamine
Amine is directly pyrolyzed obtained carbonitride and shows the block structure compacted, this is accumulated by the lamella of exhibiting high surface densification.
Fig. 2 is honeycomb carbonitride transmission electron microscope figure (TEM) prepared by embodiment 3；It can be clearly from figure
Go out, pattern presents the hollow cavity structure of bonding.
Fig. 3 is honeycomb carbonitride transmission electron microscope figure (TEM) prepared by embodiment 4.From figure as it can be seen that largely curling
Nitridation coke build-up, construct out honey comb like hollow structure.
Honeycomb carbonitride transmission electron microscope figure (TEM) prepared by Fig. 4 embodiments 5.Similar honeycomb is presented in carbonitride
Pattern.
Fig. 5 is the N of carbonitride made from comparative example 1,2 and embodiment 32Adsorption-desorption curve graph, illustration are made for example 3
The graph of pore diameter distribution of standby honeycomb carbonitride；The specific surface area of honeycomb carbonitride is up to 389.2m2·g-1, compared to body phase
Carbonitride (19.14m2·g-1) about 20 times are improved, and there is the hole for being about 2nm or so.Honeycomb without poly-dopamine modified lithium
Shape carbonitride specific surface area is about 78.14m2·g-1。
Under the body phase carbon nitride visible ray that Fig. 6 is honeycomb carbonitride prepared by embodiment 3 and prepared by comparative example 1,2 (λ >=
400nm) photocatalytic water H2-producing capacity figure.From figure it is found that its photocatalytic water hydrogen-producing speed of honeycomb carbonitride is up to 1061.87umol
g-1·h-1, the about body phase carbon nitride (151.24umolg of the preparation of comparative example 1-1·h-1) 7 times, without poly-dopamine modified lithium
Honeycomb carbonitride be about 402.55umolg-1·h-1, this shows that by using poly-dopamine modified lithium sepiolite be template
The carbonitride of bigger serface is prepared, is remarkably improved photodissociation aquatic products hydrogen activity.
Claims (8)
1. a kind of preparation method of honeycomb carbon nitride material, it is characterised in that preparation process includes the following steps：
A) sepiolite acid is handled；
B) sepiolite poly-dopamine coating modification；
C) sepiolite of poly-dopamine coating modification is uniformly mixed with carbon nitride precursor, then high-temperature roasting；
D) removing template is removed, obtains honeycomb carbonitride.
2. the preparation method of honeycomb carbon nitride material as described in requiring right 1, it is characterised in that honeycomb carbon nitride material has
There is the hollow cavity structure of bonding.
3. a kind of preparation method of honeycomb carbon nitride material as described in requiring right 1, it is characterised in that：At the sepiolite acid
Reason is by sepiolite and hydrochloric acid or nitric acid reaction, removes impurity and increase pore volume.The sepiolite poly-dopamine coating modification
It is to react acid treated sepiolite in buffer solution with Dopamine hydrochloride, generation poly-dopamine modified lithium sepiolite；It is described
It is to react poly-dopamine coating modification sepiolite with carbon nitride precursor high-temperature roasting product with etching agent to remove removing template.
4. as right 1,3 requires a kind of preparation method of honeycomb carbon nitride material, it is characterised in that：The buffer solution
PH value be 8~9；A concentration of 1~5mg/ml of the Dopamine hydrochloride.
5. as right 1,3 requires a kind of preparation method of honeycomb carbon nitride material, it is characterised in that：The etching agent is
Hydrofluoric acid or ammonium fluoride it is any.
6. a kind of preparation method of honeycomb carbon nitride material as described in requiring right 1, it is characterised in that：The carbonitride forerunner
Body refers to melamine, urea, cyanamide, dicyandiamide any or two kinds or more of mixture.
7. as right 1,6 requires a kind of preparation method of honeycomb carbon nitride material, it is characterised in that：Poly-dopamine coats
Modified meerschaum and the mass ratio of carbon nitride precursor are 1:10~1.
8. as right 1,6,7 requires a kind of preparation method of honeycomb carbon nitride material, it is characterised in that：The high temperature roasting
Burning is in air atmosphere, and calcination temperature is 500~600 DEG C, and roasting time is 1~5 hour.
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| CN201810013728.6A CN108147380A (en) | 2018-01-08 | 2018-01-08 | A kind of preparation method of honeycomb carbonitride |
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| CN111762764A (en) * | 2020-01-15 | 2020-10-13 | 山东大学 | Carbon nitride material prepared by using cage-type polysilsesquioxane as template and preparation method and application thereof |
| CN114854230A (en) * | 2022-05-27 | 2022-08-05 | 中国科学院兰州化学物理研究所 | Nano silicon dioxide loaded graphite-like phase carbon nitride and preparation method thereof, and self-lubricating phenolic aldehyde laminated cloth bearing material and preparation method thereof |
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