CN106563481B - A kind of ultra-thin graphite phase carbon nitride photochemical catalyst of ammonification and preparation method thereof - Google Patents
A kind of ultra-thin graphite phase carbon nitride photochemical catalyst of ammonification and preparation method thereof Download PDFInfo
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- CN106563481B CN106563481B CN201610876806.6A CN201610876806A CN106563481B CN 106563481 B CN106563481 B CN 106563481B CN 201610876806 A CN201610876806 A CN 201610876806A CN 106563481 B CN106563481 B CN 106563481B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000010439 graphite Substances 0.000 title claims abstract description 109
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 109
- 238000004176 ammonification Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title description 16
- 239000000463 material Substances 0.000 claims abstract description 111
- 239000011941 photocatalyst Substances 0.000 claims abstract description 64
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 33
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010792 warming Methods 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 8
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 6
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 6
- 238000000265 homogenisation Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 229960004424 carbon dioxide Drugs 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000000919 Fourier transform infrared map Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Abstract
The invention discloses ultra-thin graphite phase carbon nitride photocatalyst materials of a kind of ammonification and preparation method thereof.It is similar to the tulle with fold, and in the gauze-like with fold, thickness is uniform, is 3-5nm；Material surface is smooth, amino group rich in.Preparation: melamine is acidified; the melamine supramolecular structure crystal protonated; then calcined under the conditions of inert protective atmosphere and graphite phase carbon nitride material be made, after through Homogenization Treatments obtain graphite phase carbon nitride photocatalyst material superfine powder；The ammonia source substance that graphite phase carbon nitride photocatalyst material superfine powder and thermal decomposition generate ammonia is placed in tube furnace; carry out logical inert gas deoxygenation processing; then ladder calcining is carried out under the conditions of inert protective atmosphere: being first warming up to 500-540 DEG C; keep the temperature 2-4h; then it is warming up to 560-600 DEG C again; and 2-3h is kept the temperature, it can be obtained after cooling.It improves photocatalysis efficiency with can dramatically, and is used for CO2Catalysis reduction has excellent photocatalysis performance.
Description
Technical field
The present invention relates to photochemical catalyst fields, and in particular to a kind of ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) light urges
Agent and preparation method thereof.
Background technique
With a large amount of consumption of fossil fuel, the gas concentration lwevel in the past few decades in atmosphere is risen rapidly, this quilt
It is considered greenhouse effects one of the main reasons.It is chemical fuel carbon dioxide conversion by artificial photo-reduction system is a kind of non-
Normal attractive method.Recent years, photocatalytic reduction of carbon oxide gradually arouse people's interest, and this method is able to reality
Now it is made to have prospect in the extreme the transfer of energy and storage.For photocatalytic reduction of carbon oxide, catalyst
Using play very important role in entire reaction process.Therefore, many individual or compound photochemical catalyst quilt
It developed using this system.Such as: titanium-based photochemical catalyst, polymer semiconductor, metal sulfide or oxide etc..
Graphite phase carbon nitride is a kind of polymer semiconductor containing only two kinds of elements of carbon nitrogen composition, steady with good heat
Qualitative, chemical stability and excellent resistance to chemical attack.In addition, suitable forbidden bandwidth (Eg=2.7eV) and leading
Band position can effectively overcome the dynamic (dynamical) barrier of carbon dioxide reduction, go on smoothly photoreduction.However, due to block
Carbonitride specific surface area it is lower and electron-hole recombination rate is very high, photocatalysis efficiency also tends to very low.Therefore, many
Research is dedicated to improving photocatalysis efficiency, such as: surface is modified, Material cladding, doping and pattern control etc..Nowadays, two-dimentional
Carbonitride is extensively studied due to significant quantum effect and unique electronic structure.In general synthesis carbonitride two
It ties up in materials process, some physics or chemical method is often employed in this synthetic system.However, due to nitridation
There are stronger π-π * interaction between carbon-coating, general physical method is difficult to obtain good effect, such as supercritical ultrasonics technology.And
The thining method (such as method of concentrated acid processing) of chemistry can destroy nitridation carbon surface amine groups abundant, this is particularly disadvantageous in two
The absorption and reduction of carbonoxide, or even reduce catalytic performance.Therefore seek a kind of novel graphite phase carbon nitride photochemical catalyst,
CO can be effectively realized2The research hotspot for transforming into the field.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of ammonification
Ultra-thin graphite phase carbon nitride (g-C3N4) photochemical catalyst and preparation method thereof, catalyst surface amino group rich in, table
Reveal significant CO2Absorption property, while there is excellent photocatalytic activity and stability.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of ultra-thin graphite phase carbon nitride (g-C of ammonification is provided3N4) photocatalyst material, it is similar to the thin of fold
Yarn, in the gauze-like with fold, thickness is uniform, is 3-5nm (as shown in Figure 2)；Material surface is smooth, and fragmentation is less,
Amino group (shown in Fig. 4) rich in,
The present invention also provides above-mentioned ultra-thin graphite phase carbon nitride (g-C3N4) photocatalyst material preparation method, including
Following steps:
(1) melamine is acidified, the melamine supramolecular structure crystal protonated, is then protected in inertia
Protect to calcine under atmospheric condition and graphite phase carbon nitride material be made, after through Homogenization Treatments obtain graphite phase carbon nitride (g-C3N4)
Photocatalyst material superfine powder；
(2) by graphite phase carbon nitride (g-C3N4) photocatalyst material superfine powder and thermal decomposition generate the ammonia source of ammonia
Substance is placed in tube furnace, carries out logical inert gas deoxygenation processing, ladder calcining is then carried out under the conditions of inert protective atmosphere:
It is first warming up to 500-540 DEG C, 2-4h is kept the temperature, is then warming up to 560-600 DEG C again, and keep the temperature 2-3h, ammonification can be obtained after cooling
Ultra-thin graphite phase carbon nitride (g-C3N4) photocatalyst material.
According to the above scheme, ammonia source substance and graphite phase carbon nitride powder quality ratio are 1:1-3 in the step (2).
According to the above scheme, the heating rate that 500-540 DEG C is warming up in the step (2) is 1-5 DEG C/min.
It is preferred that heated up calcining with relatively slow heating rate, unreacted presoma can be made further be condensed in powder and gathered
It closes, promotes its degree of polymerization.
According to the above scheme, 560-600 DEG C of heating rate >=15 DEG C/min is warming up in the step (2).With faster
Speed heating, can provide stronger thermal shock, to provide the carbonitride of stratiform to enough power from the removing of its powder, so that
Better effect is thinned.
According to the above scheme, it is ammonium sulfate or ammonium chloride that the thermal decomposition, which generates the substance of ammonia,.
According to the above scheme, acidification is formed in the step (1) for melamine solid to be dissolved in ethanol solution
Clear solution is handled with dust technology, obtains white precipitate insoluble matter, and then filtering vacuum is dry, the melamine protonated
Amine supramolecular structure crystal, it is spare；
According to the above scheme, the nitric acid solution concentration is 0.2-1mol/L, is best with 0.5mol/L concentration.Use nitric acid
Solution handles melamine to obtain the supramolecular structured crystal of melamine, and then passes through protective gas atmosphere using the crystalline solid
The lower resulting nitridation toner body condensation degree of dissolved of calcining is high, less containing non-polycondensation ingredient, mainly sends out during subsequent be thinned
Raw thinning process, this, which is very beneficial for being thinned, obtains the graphite phase carbon nitride sheet of non-porous structure, and reaches present invention invention
By using the purpose of the less ultrathin nanometer piece of the precursor preparation defect of crystalline state.
According to the above scheme, the calcination temperature in the step (1) is 530-560 DEG C, soaking time 2-4h.By above-mentioned side
Case, the homogenization processing are placed in a beaker for the graphite phase carbon nitride for obtaining calcining, are added under stirring condition a certain amount of
Alcohol form it into sticky emulsion, the emulsion is then placed in ball milling 18-24h in ball mill, after by gained
Sample vacuum drying；
According to the above scheme, the emulsion concentration is 0.5-1.5g/ml.
The beneficial effects of the present invention are:
1, the ultra-thin graphite phase carbon nitride (g-C of ammonification provided by the invention3N4) photocatalyst material has more than powder body material
The quantity (see Fig. 4) of more surface amino groups groups, CO2Absorption test shows it to CO (shown in Fig. 6)2There is strong adsorption capacity；It compares
For, ultra-thin graphite phase carbon nitride, with small, has the sound of stronger photoelectric current to photoelectronic scattered color effect under the same terms
It answers, therefore can effectively promote the separation of photo-generate electron-hole pair, to improve photocatalysis efficiency significantly, be used for CO2It urges
Changing reduction has excellent photocatalysis performance (as shown in Figure 7).
2. ultra-thin graphite phase carbon nitride (g-C provided by the invention3N4) photocatalyst material using program-controlled calcination method prepare,
Without hydro-thermal reaction, the uniform ultra-thin graphite phase carbon nitride (g-C of thickness can obtained3N4) photocatalyst material realizes simultaneously
Ammonification function, easy to operate, raw material are easy to get, without complex device, low production cost.
The micro-structure of graphite phase carbon nitride powder is formed by two-dimensional layer planar, stacked, leans on Van der Waals between layers
Power connection, this is very similar to graphite (being made of the graphene of two-dimensional stratiform).The present invention is by using ladder-elevating temperature method,
One step-up temperature to one relatively low 500-540 DEG C of temperature range, can mainly make in powder unreacted presoma into
One step condensation polymerization is promoted its degree of polymerization, is preferably heated up and calcined with relatively slow heating rate, reduced subsequent heat and subtract
Also thinned (carbonitride that substantially polycondensation has been got well is decomposed) mistake is performed etching while will continue to polycondensation in thin process
Journey, the interaction of the two processes, so that final gained carbonitride lamella fragmentation, then heats to 560-600 DEG C, herein
Ammonia molecule can enter the interlayer of graphite phase carbon nitride under high temperature, to weaken Van der Waals force between layers, forcing layer
It is separated between layer, further, it is preferable to (be not less than 15 DEG C of min using comparatively faster heating rate-1), higher heating speed
Rate can provide stronger thermal shock, to provide the carbonitride of stratiform to enough power from the removing of its powder, so that its
Layer structure is more easily peelable.
Detailed description of the invention
Fig. 1 is the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the embodiment of the present invention 13N4) photocatalyst material sweeps
Retouch electron microscopic picture；
Fig. 2 is the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the embodiment of the present invention 13N4) photocatalyst material original
Sub- force microscope picture；
Fig. 3 is the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the embodiment of the present invention 13N4) photocatalyst material (NS-
) and the XRD diffraction pattern of carbonitride powder body material (bulk-CN) CN；
Fig. 4 is the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the embodiment of the present invention 13N4) photocatalyst material (NS-
) and the FTIR map of carbonitride powder body material (bulk-CN) CN；
Fig. 5 is the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the embodiment of the present invention 13N4) photocatalyst material (NS-
CN) with the UV map of its carbonitride powder body material, wherein a is the ultra-thin graphite phase carbon nitride (g- of ammonification prepared by embodiment 1
C3N4) photocatalyst material (NS-CN), b is carbonitride powder body material (bulk-CN), and the illustration in figure is passed through by UV data
The energy map that Kubelka-Munk is equations turned and comes, wherein NS-CN is the prepared ultra-thin graphite phase carbon nitride of ammonification,
Bulk-CN is graphite-phase powder body material；
Fig. 6 is the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the embodiment of the present invention 13N4) photocatalyst material (NS-
CN) with the CO of its carbonitride powder body material2Absorption property map；
Fig. 7 is the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the embodiment of the present invention 13N4) photocatalyst material and block
The photocatalysis performance curve of body graphite phase carbon nitride material；
Fig. 8 is graphite phase carbon nitride (g-C prepared by comparative example 13N4) material FESEM figure；
Fig. 9 is graphite phase carbon nitride (g-C prepared by comparative example 23N4) material FESEM figure；
Figure 10 is graphite phase carbon nitride (g-C prepared by comparative example 33N4) the ultra-thin stone of ammonification for preparing of material and embodiment 1
Black phase carbon nitride (g-C3N4) photocatalyst material (NS-CN) FTIR scheme control；
Figure 11 is graphite phase carbon nitride (g-C prepared by comparative example 43N4) the ultra-thin stone of ammonification for preparing of material and embodiment 1
Black phase carbon nitride (g-C3N4) photocatalyst material (NS-CN) FESEM scheme control；
Figure 12 is graphite phase carbon nitride (g-C prepared by comparative example 53N4) the ultra-thin stone of ammonification for preparing of material and embodiment 1
Black phase carbon nitride (g-C3N4) photocatalyst material (NS-CN) FESEM scheme control.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing to the present invention make into
One step detailed description.
Embodiment 1
1) presoma is handled: melamine solid being dissolved in ethanol solution and forms clear solution, is then added dropwise
The nitric acid solution of 0.5M has white precipitate generation, then by this white precipitate filtering vacuum drying for standby；
2) block graphite phase carbon nitride (g-C is prepared3N4) photocatalyst material: the resulting white depositions of step 1) are moved
Into crucible, then crucible is placed in Muffle furnace and is warming up to 550 DEG C with the heating rate of 20 DEG C/min, and keeps the temperature 3h, it is cold
But faint yellow solid is obtained afterwards；
3) graphite phase carbon nitride (g-C is prepared3N4) photocatalyst material superfine powder: by the resulting yellowish color lump of step 2)
Body graphite phase carbon nitride (g-C3N4) be placed in a beaker, it is 1g/ml milkiness that a certain amount of alcohol is added under stirring condition and forms concentration
Then the emulsion is placed in ball mill ball milling for 24 hours by liquid, after gained sample is dried in vacuo；
4) the ultra-thin graphite phase carbon nitride (g-C of ammonification is prepared3N4) photocatalyst material: after ball milling drying in step 3)
Powder and ammonium sulfate or ammonium chloride (mass ratio 1:2) be placed in tube furnace, pass first into argon gas 30min deoxygenation, then
Gradient increased temperature is set under the conditions of logical argon gas, is first warming up to 520 DEG C with 1-5 DEG C/min heating rate, and keep the temperature 3h, then again with
20 DEG C/min heating rate is warming up to 580 DEG C, and keeps the temperature 3h, and the ultra-thin graphite phase carbon nitride (g- of ammonification can be obtained after cooling
C3N4) photocatalyst material.
It is super after being finally thinned since the thermal shock to block materials is insufficient when second stage heating rate is too small
Part block materials can be contained in thin slice, i.e. the graphite phase carbon nitride percentage of ultrathin nanometer structure reduces, photocatalytic activity
Also it decreases.
Photocatalysis experiment: by the ultra-thin graphite phase carbon nitride (g-C of prepared ammonification3N4) photocatalyst material photocatalysis
Test: taking 100mg sample that volume is added uniform in the reactor of 160ml, to add a small amount of water ultrasonic disperse, then that this is anti-
It answers device (containing sample) to be placed in 80 DEG C of baking oven and dries 12h, later, take out reactor and seal, be then first passed through the nitrogen of 30min
Gas, then it is passed through the CO of 3.5ml2Gas, finally by the Xe light of reactor 300W according to sampling and testing after 1h.
Experiment condition in accordance with the above-mentioned embodiment 1 can prepare the graphite-phase nitrogen of the more uniform and more excellent catalytic performance of pattern
Change carbon superthin section, characterization and photocatalysis result are as follows:
It is as shown in Figure 1 the ultra-thin graphite phase carbon nitride (g-C of ammonification of preparation prepared by the present embodiment3N4) photochemical catalyst
The scanning electron microscopic picture of material, as seen from the figure, the ultra-thin graphite phase carbon nitride (g-C of prepared ammonification3N4) photocatalyst material is in
Show the ultra-thin form of fold, there is no porous structure on superthin section, hole defect is less, similar to ultra-thin graphene-structured.
It is illustrated in figure 2 the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the present embodiment3N4) photocatalyst material
Atomic force microscope images, as seen from the figure, the ultra-thin graphite phase carbon nitride (g-C of prepared ammonification3N4) photocatalyst material thickness
For 3nm-4nm.
It is illustrated in figure 3 the ultra-thin graphite phase carbon nitride (g-C of ammonification of preparation prepared by the present embodiment3N4) photochemical catalyst
Material (NS-CN) and carbonitride powder body material (directly 550 DEG C of 2h are calcined in air by melamine presoma to obtain,
Bulk-CN XRD diffraction pattern), as seen from the figure, the ultra-thin graphite phase carbon nitride (g-C of prepared ammonification3N4) photocatalyst material
Diffraction maximum and block materials it is almost the same, the embodiment of the present invention preparation the ultra-thin graphite phase carbon nitride of ammonification be in the angle of diffraction
There is a blunt and wideization diffraction maximum at 20-30 °, illustrates the ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) photocatalyst material deposits
In the structure of unformed shape.
It is illustrated in figure 4 the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the present embodiment3N4) photocatalyst material
(NS-CN) and the FTIR map of carbonitride powder body material, as seen from the figure, the ultra-thin graphite phase carbon nitride (g- of prepared ammonification
C3N4) photocatalyst material absorption peak peak and block materials it is almost the same, further illustrate both basic molecular structure it is consistent
Property, however, for ultra-thin graphite phase carbon nitride (g-C3N4) photocatalyst material absorption map, in 3100-3400cm-1In range
Absorption is remarkably reinforced, this partially absorbs the vibration that vibration belongs to the hydrogen bound to nitrogen of amino, illustrates surface ammonification success.
It is illustrated in figure 5 the ultra-thin graphite phase carbon nitride (g-C of ammonification of preparation prepared by the present embodiment3N4) photochemical catalyst
The UV map of material (NS-CN) and carbonitride powder body material, as seen from the figure, the ultra-thin graphite phase carbon nitride (g- of the ammonification of preparation
C3N4) apparent blue shift occurs in the Absorption edge of photocatalyst material, this is mainly that there are quantum in ultra-thin graphite phase carbon nitride
Caused by dimensional effect；The blue shift of its Absorption edge also illustrates that its forbidden bandwidth broadens, and it is obvious that effect is thinned in side illustration.
It is illustrated in figure 6 the ultra-thin graphite phase carbon nitride (g-C of ammonification of preparation prepared by the present embodiment3N4) photochemical catalyst
The CO of material (NS-CN) and carbonitride powder body material2Absorption property figure.As seen from the figure, the ultra-thin graphite-phase nitridation of the ammonification of preparation
Carbon (g-C3N4) photocatalyst material CO2Absorption property is significantly increased than powder carbonitride, this is mainly due to its high specific surface
Amino more than long-pending and surface, and basic amine group can be with acid CO2Molecule is formed on its surface chemisorption, to improve CO2
Absorption property, effective CO2Absorption is enhancing photocatalysis CO2The basis of reduction.
It is illustrated in figure 7 the ultra-thin graphite phase carbon nitride (g-C of ammonification manufactured in the present embodiment3N4) photocatalyst material (NS-
) and the photocatalysis CO of block materials (bulk-CN) CN2Also original image, as seen from the figure, the ultra-thin graphite phase carbon nitride of prepared ammonification
(g-C3N4) photocatalyst material and block materials product be all methanol and methane, however, the ultra-thin graphite phase carbon nitride (g- of ammonification
C3N4) photochemical catalyst catalysis restore CO2Significant effect is better than block materials performance.
Comparative example 1
Substantially the same manner as Example 1, powder and ammonium sulfate mass ratio after only ball milling is dry in step 3) are 1:0.3.
It is characterized, sees Fig. 8:
Image is characterized by FESEM considerable not subtract it is found that being also mixed in the graphite phase carbon nitride material of above-mentioned preparation
Thin block pattern, this may be reduced reaction system due to ammonium sulfate additional amount and generate ammonia reduction, cause that insufficient cause is thinned
's.Simultaneously as a large amount of presence of block reduce the system photocatalysis performance compared to embodiment 1.
Comparative example 2
Substantially the same manner as Example 1, powder and ammonium sulfate mass ratio after only ball milling is dry in step 3) are 5:1.
It is characterized, sees Fig. 9:
By FESEM characterization image it is found that the graphite phase carbon nitride material ammonia offer amount of above-mentioned preparation is relatively excessive, so that
It is broken that superthin section is thinned, thus decreases catalytic performance also.
Comparative example 3
It is substantially the same manner as Example 1, only regulate and control the target temperature of gradient increased temperature first stage in step 3) less than 480
℃。
Through characterizing:
By upper figure FTIR map (see Figure 10) it is found that NBs-CN is the FTIR of 3 gained sample of comparative example as a result, Bulk-CN
The FTIR map of conventional calcination melamine powder, as a result, it has been found that, when the target temperature of first stage is lower than 500 DEG C, gained is produced
Some are different for object and target product (graphite phase carbon nitride), there is the ingredient of incomplete polycondensation in product, i.e., so-called containing miscellaneous
Matter, when target temperature is higher than 550 DEG C, polycondensation excessively reduces yield.So first stage temperature is preferably higher than 500
DEG C, but this stage mainly allows non-polycondensation ingredient polycondensation again, therefore temperature cannot be excessively high, preferably 500-540 DEG C is compared conjunction
It is suitable.
Comparative example 4
It is substantially the same manner as Example 1, the target temperature of gradient increased temperature second stage is only changed, the temperature is controlled and is less than
580 DEG C or it is greater than 600 DEG C, experimental result discovery, when target temperature is lower than 580 DEG C, ultrathin nanometer structure in final sample
Graphite phase carbon nitride percentage compared to embodiment 1 reduce (as shown in the FESEM of Figure 11 compare, left figure be this comparative example product,
Right figure is the product of embodiment 1), this may be since temperature is lower, and ammonia there is no enough kinetic energy and enter graphite-phase
Between carbon nitride layer, it is unfavorable for removing；
And when temperature is greater than 600 DEG C, ultra-thin graphite phase carbon nitride is almost decomposed, almost without target product.
Comparative example 5
It is substantially the same manner as Example 1, the soaking time of gradient increased temperature second stage is only changed, the experimental results showed that,
When soaking time is less than 2h, the graphite phase carbon nitride percentage of ultrathin nanometer structure reduces (such as compared to embodiment 1 in final sample
Comparison shown in the FESEM of Figure 12, left figure are the product of the present embodiment, and right figure is the product of embodiment 1), this may be due to ammonia
Time of contact is shorter at high temperature with block materials for gas, and ammonia does not have fully penetrated graphite phase carbon nitride interlayer, also the same unfavorable
In being completely exfoliated；When temperature is greater than 3h, the fragile part (such as rejected region) of part superthin section can be etched by ammonia, so that
Superthin section is destroyed), in addition increase highly energy-consuming, it is uneconomical.
Comparative example 6
In embodiment 2 change processing presoma nitric acid concentration, using 0.1M nitric acid treatment melamine presoma when,
It obtains being white flocculent deposit, the precipitated crystal performance of the type is poor, and the nitridation toner body obtained after calcining does not gather
The ingredient of conjunction is on the high side, unfavorable to being further thinned.
Comparative example 7
In embodiment 2 change processing presoma nitric acid concentration, using 3M nitric acid treatment melamine presoma when, by
There is strong oxidisability in relatively dense nitric acid, so that forerunner's body portion starts to aoxidize, it is good super that crystallinity will be cannot get
The presoma of molecular structure.
Embodiment 2
1) presoma is handled: melamine solid being dissolved in ethanol solution and forms clear solution, is then added dropwise
The nitric acid solution of 0.5M has white precipitate generation, then by this white precipitate filtering vacuum drying for standby；
2) block graphite phase carbon nitride (g-C is prepared3N4) photocatalyst material: the resulting white depositions of step 1) are moved
Into crucible, then crucible is placed in Muffle furnace and is warming up to 560 DEG C with the heating rate of 20 DEG C/min, and keeps the temperature 3h, it is cold
But faint yellow solid is obtained afterwards；
3) graphite phase carbon nitride (g-C is prepared3N4) photocatalyst material superfine powder: by the resulting yellowish color lump of step 2)
Body graphite phase carbon nitride (g-C3N4) be placed in a beaker, it is 0.5g/ml cream that a certain amount of alcohol is added under stirring condition and forms concentration
Then the emulsion is placed in ball mill ball milling for 24 hours by turbid, after gained sample is dried in vacuo；
4) the ultra-thin graphite phase carbon nitride (g-C of ammonification is prepared3N4) photocatalyst material: after ball milling drying in step 3)
Powder and ammonium sulfate or ammonium chloride (mass ratio 1:1.5) be placed in tube furnace, pass first into argon gas 30min deoxygenation, so
Gradient increased temperature is set under the conditions of logical argon gas afterwards, is first warming up to 540 DEG C with 1-5 DEG C/min heating rate, and keep the temperature 2h, then again
600 DEG C are warming up to 15 DEG C/min heating rate, and keeps the temperature 3h, the ultra-thin graphite phase carbon nitride (g- of ammonification can be obtained after cooling
C3N4) photocatalyst material.
The characterizing method of reference implementation example 1 is characterized, phenetic analysis explanation: the ultra-thin graphite of ammonification prepared by embodiment
Phase carbon nitride (g-C3N4) photocatalyst material present fold ultra-thin form, superthin section upper surface is smooth, does not have porous structure, hole
Defect is less, similar to ultra-thin graphene-structured.Thickness is uniform, is 3nm-5nm.
Ultra-thin graphite phase carbon nitride (the g-C of ammonification prepared by XRD characterization analytic explanation book3N4) photocatalyst material spreads out
It is almost the same with block materials to penetrate peak, and the ultra-thin graphite phase carbon nitride of ammonification manufactured in the present embodiment is when the angle of diffraction is 20-30 °
There is a blunt and wideization diffraction maximum, illustrates the ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) there are unformed for photocatalyst material
The structure of state.
IR Characterization analytic explanation: the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the present embodiment3N4) photochemical catalyst
The absorption peak peak and block materials of material are almost the same, further illustrate the two basic molecular structure consistency, however, for super
Thin graphite phase carbon nitride (g-C3N4) photocatalyst material absorption map, in 3100-3400cm-1It absorbs and is remarkably reinforced in range,
This partially absorbs the vibration that vibration belongs to the hydrogen bound to nitrogen of amino, illustrates surface ammonification success.
Embodiment 3
1) presoma is handled: melamine solid being dissolved in ethanol solution and forms clear solution, is then added dropwise
The nitric acid solution of 0.5M has white precipitate generation, then by this white precipitate filtering vacuum drying for standby；
2) block graphite phase carbon nitride (g-C is prepared3N4) photocatalyst material: the resulting white depositions of step 1) are moved
Into crucible, then crucible is placed in Muffle furnace and is warming up to 530 DEG C with the heating rate of 20 DEG C/min, and keeps the temperature 4h, it is cold
But faint yellow solid is obtained afterwards；
3) graphite phase carbon nitride (g-C is prepared3N4) photocatalyst material superfine powder: by the resulting yellowish color lump of step 2)
Body graphite phase carbon nitride (g-C3N4) be placed in a beaker, it is 1.5g/ml cream that a certain amount of alcohol is added under stirring condition and forms concentration
Then the emulsion is placed in ball milling 20h in ball mill by turbid, after gained sample is dried in vacuo；
4) the ultra-thin graphite phase carbon nitride (g-C of ammonification is prepared3N4) photocatalyst material: after ball milling drying in step 3)
Powder and ammonium sulfate or ammonium chloride (mass ratio 1:3) be placed in tube furnace, argon gas deoxygenation is passed first into, then in logical argon
Gradient increased temperature is set under gas bar part, is first warming up to 510 DEG C with 1-5 DEG C/min heating rate, and keep the temperature 3h, then again with 15 DEG C/
Min heating rate is warming up to 560 DEG C, and keeps the temperature 3h, and the ultra-thin graphite phase carbon nitride (g-C of ammonification can be obtained after cooling3N4) light urges
Agent material.
The characterizing method of reference implementation example 1 is characterized, phenetic analysis explanation: the ultra-thin graphite of ammonification prepared by embodiment
Phase carbon nitride (g-C3N4) photocatalyst material present fold ultra-thin form, superthin section upper surface is smooth, does not have porous structure, hole
Defect is less, similar to ultra-thin graphene-structured.Thickness is uniform, is 3nm-5nm.
Ultra-thin graphite phase carbon nitride (the g-C of ammonification prepared by XRD characterization analytic explanation book3N4) photocatalyst material spreads out
It is almost the same with block materials to penetrate peak, and the ultra-thin graphite phase carbon nitride of ammonification manufactured in the present embodiment is when the angle of diffraction is 20-30 °
There is a blunt and wideization diffraction maximum, illustrates the ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) there are unformed for photocatalyst material
The structure of state.
IR Characterization analytic explanation: the ultra-thin graphite phase carbon nitride (g-C of ammonification prepared by the present embodiment3N4) photochemical catalyst
The absorption peak peak and block materials of material are almost the same, further illustrate the two basic molecular structure consistency, however, for super
Thin graphite phase carbon nitride (g-C3N4) photocatalyst material absorption map, in 3100-3400cm-1It absorbs and is remarkably reinforced in range,
This partially absorbs the vibration that vibration belongs to the hydrogen bound to nitrogen of amino, illustrates surface ammonification success.
Claims (8)
1. a kind of ultra-thin graphite phase carbon nitride photocatalyst material of ammonification, it is characterised in that: it is in the gauze-like with fold, and
The ultra-thin graphite phase carbon nitride on piece of ammonification does not have porous structure, and thickness is uniform, is 3-5nm；Material surface is smooth, containing abundant
Amino group.
2. a kind of preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification, it is characterised in that: including following step
It is rapid:
(1) melamine is acidified, the melamine supramolecular structure crystal protonated, then protects gas in inertia
Calcined under the conditions of atmosphere and graphite phase carbon nitride material be made, after through Homogenization Treatments obtain graphite phase carbon nitride (g-C3N4) light urges
Agent material superfine powder；
(2) the ammonia source substance that graphite phase carbon nitride photocatalyst material superfine powder and thermal decomposition generate ammonia is placed in tubular type
In furnace, logical inert gas deoxygenation processing is carried out, ladder calcining is then carried out under the conditions of inert protective atmosphere: being first warming up to 500-
540 DEG C, 2-4h is kept the temperature, is then warming up to 560-600 DEG C again, and keep the temperature 2-3h, the ultra-thin graphite-phase of ammonification can be obtained after cooling
Carbon nitride photocatalyst material；
The heating rate that 500-540 DEG C is warming up in the step (2) is 1-5 DEG C/min；560- is warming up in the step (2)
600 DEG C of heating rate >=15 DEG C/min.
3. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 2, feature
Be: thermal decomposition generates the ammonia source substance of ammonia in the step (2) and graphite phase carbon nitride powder quality ratio is 1:1-3.
4. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 2, feature
Be: the ammonia source substance that the thermal decomposition generates ammonia is ammonium sulfate or ammonium chloride.
5. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 2, feature
Be: acidification forms clear solution for melamine solid to be dissolved in ethanol solution in the step (1), with dilute nitre
Acid processing, obtains white precipitate insoluble matter, and then filtering vacuum is dry, and the melamine supramolecular structure protonated is brilliant
Body, it is spare.
6. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 5, feature
Be: the dilute nitric acid solution concentration is 0.2-1mol/L.
7. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 2, feature
Be: the calcination temperature in the step (1) is 530-560 DEG C, soaking time 2-4h.
8. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 2, feature
Be: the Homogenization Treatments in the step (1) are that the graphite phase carbon nitride for obtaining calcining is placed in a beaker, stirring condition
Lower a certain amount of alcohol of addition forms it into sticky emulsion, and the emulsion is then placed in ball milling 18-24h in ball mill,
After gained sample is dried in vacuo.
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