CN106563481A - Ammoniated ultrathin graphite-phase carbonitride photocatalyst and preparation method thereof - Google Patents
Ammoniated ultrathin graphite-phase carbonitride photocatalyst and preparation method thereof Download PDFInfo
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- CN106563481A CN106563481A CN201610876806.6A CN201610876806A CN106563481A CN 106563481 A CN106563481 A CN 106563481A CN 201610876806 A CN201610876806 A CN 201610876806A CN 106563481 A CN106563481 A CN 106563481A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 121
- 239000000843 powder Substances 0.000 claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 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
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 109
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 109
- 239000010439 graphite Substances 0.000 claims description 105
- 229910002804 graphite Inorganic materials 0.000 claims description 105
- 238000004176 ammonification Methods 0.000 claims description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000010792 warming Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 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 group 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
- 239000007789 gas Substances 0.000 claims description 7
- 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
- 238000000265 homogenisation Methods 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 150000002835 noble gases Chemical class 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
- 239000000126 substance Substances 0.000 abstract description 4
- 229920000877 Melamine resin Polymers 0.000 abstract description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 150000007974 melamines Chemical class 0.000 abstract 1
- 230000037303 wrinkles Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 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 12
- 239000000047 product Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000000445 field-emission scanning electron microscopy Methods 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
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229960004424 carbon dioxide Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000012360 testing method 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
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect 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
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 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
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 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
- 239000004065 semiconductor Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 241000292525 Titanio 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
- 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method 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
- 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000011148 porous material 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
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 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 an ammoniated ultrathin graphite-phase carbonitride photocatalyst material and a preparation method thereof. The ammoniated ultrathin graphite-phase carbonitride photocatalyst material resembles wrinkled tulle, is in the shape of tulle with wrinkles and has a uniform thickness of 3 to 5 nm; and the surface of the material is smooth and contains rich amino groups. The preparation method comprises the following steps: acidifying melamine so as to obtain a protonated melamine supermolecular structure crystal, carrying out calcining in an inert protective atmosphere so as to prepare a graphite-phase carbonitride material and carrying out uniformization so as to obtain ultrafine powder of a graphite-phase carbonitride photocatalyst material; and placing the ultrafine powder of the graphite-phase carbonitride photocatalyst material and an ammonia-source substance capable of producing ammonia gas through thermal decomposition into a tubular furnace, introducing inert gas for deoxygenation and then carrying out gradient calcining in the inert protective atmosphere, i.e., carrying out heating to 500 to 540 DEG C at first, maintaining the temperature for 2 to 4 h, then carrying out heating to 560 to 600 DEG C, maintaining the temperature for 2 to 3 h and then carrying out cooling. The ammoniated ultrathin graphite-phase carbonitride photocatalyst material has substantially improved photocatalysis efficiency and present excellent photocatalysis performance when applied to catalytic reduction of CO2.
Description
Technical field
The present invention relates to photocatalyst field, 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 technology
With a large amount of consumption of Fossil fuel, the gas concentration lwevel in the past few decades in air rises rapidly, this quilt
It is considered greenhouse effect one of the main reasons.It is a kind of non-for chemical fuel carbon dioxide conversion by artificial photo-reduction system
Normal attractive method.Recent years, photocatalytic reduction of carbon oxide gradually arouse people's interest, and this method is able to reality
Now which is caused to have prospect in the extreme the transfer of energy and storage.For photocatalytic reduction of carbon oxide, catalyst
Using very important role is play in whole course of reaction.Therefore, many single or compound photocatalyst quilt
Develop using this system.For example：Titanio photocatalyst, polymer semiconductor, metal sulfide or oxide etc..
Graphite phase carbon nitride is a kind of containing only two kinds of elementary composition polymer semiconductors of carbon nitrogen, and which has good heat steady
Qualitative, chemical stability and excellent resistance to chemical attack.Additionally, suitable energy gap (Eg=2.7eV) and leading
Band position can effectively overcome the dynamic (dynamical) barrier of carbon dioxide reduction, be smoothed out photoreduction.However, due to block
Carbonitride specific surface area it is relatively low and electron-hole recombination rate is very high, its photocatalysis efficiency also tends to very low.Therefore, it is many
Research is devoted to improving photocatalysis efficiency, for example：Surface is modified, Material cladding, doping and morphology control etc..Nowadays, two dimension
Carbonitride is extensively studied due to significant quantum effect and unique electronic structure.In general synthesis carbonitride two
In dimension materials process, some physics or chemistry method is often employed in this synthetic system.However, due to nitridation
There is stronger π-π * to interact between carbon-coating, general physical method is difficult to obtain good effect, such as supercritical ultrasonics technology.And
The thining method (method that for example concentrated acid is processed) of chemistry can destroy the abundant amine groups of nitridation carbon surface, and this is particularly disadvantageous in two
The absorption and reduction of carbonoxide, or even reduce catalytic performance.Therefore seek a kind of new graphite phase carbon nitride photocatalyst,
CO can be effectively realized2The study hotspot for transforming into the field.
The content of the invention
The technical problem to be solved is for above-mentioned deficiency present in prior art, there is provided a kind of ammonification
Ultra-thin graphite phase carbon nitride (g-C3N4) photocatalyst and preparation method thereof, the catalyst surface contains abundant amino group, table
Reveal significant CO2Absorption property, while with excellent photocatalytic activity and stability.
To solve above-mentioned technical problem, the technical solution used in the present invention is：
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 homogeneous, is 3-5nm (as shown in Figure 2)；Material surface is smooth, and fragmentation is less,
Containing abundant amino group (shown in Fig. 4),
Present invention also offers above-mentioned ultra-thin graphite phase carbon nitride (g-C3N4) photocatalyst material preparation method, including
Following steps：
(1) tripolycyanamide is acidified, obtains the tripolycyanamide supramolecular structure crystal for protonating, then protect in inertia
Calcining under shield atmospheric condition is obtained graphite phase carbon nitride material, after Jing 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 produce the ammonia source of ammonia
Material is placed in tube furnace, is carried out logical noble gases deoxygenation and is processed, and ladder calcining is then carried out under the conditions of inert protective atmosphere：
500-540 DEG C is first warming up to, 2-4h is incubated, is then warming up to 560-600 DEG C again, and is incubated 2-3h, ammonification after cooling, can be obtained
Ultra-thin graphite phase carbon nitride (g-C3N4) photocatalyst material.
By such scheme, in the step (2), ammonia source material and graphite phase carbon nitride powder quality ratio are 1:1-3.
By such 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 heat up calcining with relatively slow heating rate, unreacted presoma in powder body can be made further to be condensed poly-
Close, lift its degree of polymerization.
By such scheme, 560-600 DEG C of heating rate >=15 DEG C/min in the step (2), is warming up to.With faster
Speed heats up, and can provide stronger thermal shock, provides enough power for the carbonitride of stratiform is peeled off from its powder body so that
It is thinning better.
By such scheme, it is ammonium sulfate or ammonium chloride that described thermal decomposition produces the material of ammonia,.
By such scheme, in the step (1), acidifying is that tripolycyanamide solid dissolving is formed in ethanol solution
Settled solution, with dust technology process, obtains white precipitate insoluble matter, and then filtering vacuum is dried, and obtains the melamine for protonating
Amine supramolecular structure crystal, it is standby；
By such scheme, the salpeter solution concentration is 0.2-1mol/L, is optimal with 0.5mol/L concentration.Using nitric acid
Solution obtains the supramolecular structured crystal of tripolycyanamide to tripolycyanamide process, and then passes through protective gas atmosphere using the crystalline solid
Nitridation toner body condensation degree of dissolved obtained by lower calcining is high, less containing non-polycondensation composition, mainly sends out during subsequently thinning
Raw thinning process, this is very beneficial for the thinning graphite phase carbon nitride sheet for obtaining non-multi pore structure, and reaches present invention invention
The purpose of the less ultrathin nanometer piece of defect is prepared by using the presoma of crystalline state.
By such scheme, the calcining heat in the step (1) is 530-560 DEG C, and temperature retention time is 2-4h.By above-mentioned side
Case, described homogenization are processed as the graphite phase carbon nitride that calcining is obtained is placed in beaker, add a certain amount of under stirring condition
Ethanol form it into sticky emulsion, the emulsion is placed in into ball milling 18-24h in ball mill then, by gained after terminating
Sample is vacuum dried；
By such scheme, described emulsion concentration is 0.5-1.5g/ml.
The beneficial effects of the present invention is：
1st, the ultra-thin graphite phase carbon nitride (g-C of the ammonification that the present invention is provided3N4) photocatalyst material has more than powder body material
The quantity (see Fig. 4) of many surface amino groups groups, CO2Absorption test shows which to CO (shown in Fig. 6)2There is strong absorbability；Compare
For, ultra-thin graphite phase carbon nitride is acted on to photoelectronic scattered color with little, the sound with higher photoelectric current under the same terms
Should, therefore, it is possible to be effectively facilitated the separation of photo-generate electron-hole pair, so as to significantly increase photocatalysis efficiency, for CO2Urge
Change reduction with excellent photocatalysis performance (as shown in Figure 7).
2. the ultra-thin graphite phase carbon nitride (g-C that the present invention is provided3N4) photocatalyst material using program control calcination method prepare,
Without the need for hydro-thermal reaction, you can obtaining the homogeneous ultra-thin graphite phase carbon nitride (g-C of thickness3N4) photocatalyst material realization simultaneously
Ammonification function, easy to operate, raw material is easy to get, without the need for complex device, low production cost.
The micro structure of graphite phase carbon nitride powder body is formed by two-dimensional layer planar, stacked, between layers by Van der Waals
Power connects, and this is very similar to graphite (being made up of the Graphene of the stratiform of two dimension).The present invention by using ladder-elevating temperature method, the
One stage is warming up to relatively low temperature range 500-540 DEG C, and in can mainly making powder body, unreacted presoma enters
One step condensation polymerization, lifts its degree of polymerization, is preferably heated up with relatively slow heating rate and is calcined, is reduced subsequent heat and subtract
May proceed to while polycondensation, be also carried out thinning (carbonitride that substantially polycondensation the has been got well is decomposed) mistake of etching in thin process
Journey, the two processes interact so that final gained carbonitride lamella fragmentation, then heat to 560-600 DEG C, here
Under high temperature, ammonia molecule can enter into the interlayer of graphite phase carbon nitride, so as to weaken Van der Waals force between layers, forcing layer
Separate between layer, further, it is preferable to use comparatively faster heating rate (to be not less than 15 DEG C of min-1), higher intensification speed
Rate can provide stronger thermal shock, provide enough power for the carbonitride of stratiform is peeled off from its powder body, so that its
Layer structure is more easily peelable.
Description of the drawings
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-
CN) and carbonitride powder body material (bulk-CN) XRD diffraction patterns；
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-
CN) and carbonitride powder body material (bulk-CN) FTIR collection of illustrative plates；
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) the UV collection of illustrative plates with its carbonitride powder body material, wherein a are 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 passes through by UV data
The energy collection of illustrative plates that Kubelka-Munk is equations turned and comes, wherein NS-CN are 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) the CO with its carbonitride powder body material2Absorption property collection of illustrative plates；
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 the graphite phase carbon nitride (g-C prepared by comparative example 13N4) material FESEM figure；
Fig. 9 is the graphite phase carbon nitride (g-C prepared by comparative example 23N4) material FESEM figure；
Figure 10 is the 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 figure control；
Figure 11 is the 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 figure control；
Figure 12 is the 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 figure control.
Specific embodiment
To make those skilled in the art more fully understand technical scheme, below in conjunction with the accompanying drawings the present invention is made into
One step is described in detail.
Embodiment 1
1) presoma is processed：Tripolycyanamide solid dissolving is formed into settled solution in ethanol solution, then Deca
The salpeter solution of 0.5M, has white precipitate to produce, then by this white precipitate filtering vacuum drying for standby；
2) prepare block graphite phase carbon nitride (g-C3N4) photocatalyst material：By step 1) obtained by white depositions move
Into crucible, then crucible is positioned in Muffle furnace and 550 DEG C is warming up to the heating rate of 20 DEG C/min, and be incubated 3h, it is cold
But faint yellow solid is obtained afterwards；
3) prepare graphite phase carbon nitride (g-C3N4) photocatalyst material superfine powder：By step 2) obtained by yellowish color lump
Body graphite phase carbon nitride (g-C3N4) be placed in beaker, it is 1g/ml milkiness to add a certain amount of ethanol to form concentration under stirring condition
Then the emulsion be placed in ball milling 24h in ball mill by liquid, after terminating is vacuum dried gained sample；
4) prepare the ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) photocatalyst material：By step 3) in ball milling be dried after
Powder body and ammonium sulfate or ammonium chloride (mass ratio is 1:2) it is placed in tube furnace, passes first into argon 30min deoxygenations, then
Gradient increased temperature is set under the conditions of logical argon, first 520 DEG C is warming up to 1-5 DEG C/min heating rates, and is incubated 3h, then again with
20 DEG C/min heating rates are warming up to 580 DEG C, and are incubated 3h, and the ultra-thin graphite phase carbon nitride (g- of ammonification can be obtained after cooling
C3N4) photocatalyst material.
When second stage heating rate is too small, due to the thermal shock to block materials it is insufficient, it is final it is thinning after it is super
The graphite phase carbon nitride percentage ratio that part block materials, i.e. ultrathin nanometer structure can be contained in thin slice is reduced, its photocatalytic activity
Also decrease.
Photocatalysis are tested：By the ultra-thin graphite phase carbon nitride (g-C of prepared ammonification3N4) photocatalyst material photocatalysis
Test：During 100mg samples addition volume is taken for the reactor of 160ml, a small amount of water ultrasonic disperse is added uniformly, it is then that this is anti-
Answer device (containing sample) to be placed in 80 DEG C of baking oven and dry 12h, afterwards, 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 according to above-described embodiment 1 can prepare the graphite-phase nitrogen of the more uniform and more excellent catalytic performance of pattern
Change carbon superthin section, which characterizes and photocatalysis result is as follows：
Ultra-thin graphite phase carbon nitride (the g-C of ammonification of the preparation being illustrated in figure 1 prepared by the present embodiment3N4) photocatalyst
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
The ultra-thin form of existing fold, no loose structure on superthin section, hole defect are less, similar to ultra-thin graphene-structured.
Ultra-thin graphite phase carbon nitride (the g-C of ammonification being illustrated in figure 2 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.
Ultra-thin graphite phase carbon nitride (the g-C of ammonification of the preparation being illustrated in figure 3 prepared by the present embodiment3N4) photocatalyst
Material (NS-CN) and carbonitride powder body material (directly calcine 550 DEG C of 2h in atmosphere by tripolycyanamide presoma to obtain,
Bulk-CN XRD diffraction patterns), as seen from the figure, the ultra-thin graphite phase carbon nitride (g-C of prepared ammonification3N4) photocatalyst material
Diffraction maximum it is basically identical with block materials, the embodiment of the present invention prepare the ultra-thin graphite phase carbon nitride of ammonification in the angle of diffraction be
There is the diffraction maximum of blunt and wideization when 20-30 °, illustrate the ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) photocatalyst material deposits
In the structure of unformed shape.
Ultra-thin graphite phase carbon nitride (the g-C of ammonification being illustrated in figure 4 prepared by the present embodiment3N4) photocatalyst material
(NS-CN) and carbonitride powder body material FTIR collection of illustrative plates, as seen from the figure, the ultra-thin graphite phase carbon nitride (g- of prepared ammonification
C3N4) photocatalyst material absorption peak-to-peak it is basically identical with block materials, further illustrate both basic molecular structures consistent
Property, however, for ultra-thin graphite phase carbon nitride (g-C3N4) photocatalyst material absorption collection of illustrative plates, in 3100-3400cm-1In the range of
Absorption is remarkably reinforced, and this partially absorbs the vibration that vibration belongs to the hydrogen bound to nitrogen of amino, illustrates surface ammonification success.
Ultra-thin graphite phase carbon nitride (the g-C of ammonification of the preparation being illustrated in figure 5 prepared by the present embodiment3N4) photocatalyst
The UV collection of illustrative plates of material (NS-CN) and carbonitride powder body material, as seen from the figure, the ultra-thin graphite phase carbon nitride (g- of ammonification of preparation
C3N4) obvious blue shift occurs in the Absorption edge of photocatalyst material, there is quantum in being mainly ultra-thin graphite phase carbon nitride in this
What dimensional effect caused；The blue shift of its Absorption edge also illustrates that its energy gap broadens, and the thinning effect of side illustration is obvious.
Ultra-thin graphite phase carbon nitride (the g-C of ammonification of the preparation being illustrated in figure 6 prepared by the present embodiment3N4) photocatalyst
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 body carbonitride, and this is mainly due to its high specific surface
Amino more than product and surface, and basic amine group can be with acid CO2Molecule forms chemisorbed on its surface, so as to improve CO2
Absorption property, effective CO2Absorption is to strengthen 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-
CN) and block materials (bulk-CN) photocatalysis CO2Also artwork, 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) photocatalyst catalysis reduction CO2Effect is significant is better than block materials performance.
Comparative example 1
Substantially the same manner as Example 1, simply step 3) in the dried powder body of ball milling and ammonium sulfate mass ratio be 1：0.3.
Jing is characterized, and sees Fig. 8：
From FESEM phenogram pictures, in the graphite phase carbon nitride material of above-mentioned preparation, considerable not subtracting also is mixed with
Thin block pattern, this reduces reaction system because of ammonium sulfate addition and produces ammonia and reduces, and causes thinning insufficient cause
's.Simultaneously as a large amount of presence of block cause the system photocatalysis performance to compare embodiment 1 reducing.
Comparative example 2
Substantially the same manner as Example 1, simply step 3) in the dried powder body of ball milling and ammonium sulfate mass ratio be 5:1.
Jing is characterized, and sees Fig. 9：
From FESEM phenogram pictures, the graphite phase carbon nitride material ammonia offer amount of above-mentioned preparation is relatively excessive so that
Thinning superthin section is crushed, and catalytic performance is also decreased.
Comparative example 3
It is substantially the same manner as Example 1, simply regulate and control step 3) in the gradient increased temperature first stage target temperature be less than 480
℃。
Jing is characterized：
From upper figure FTIR collection of illustrative plates (see Figure 10), FTIR results of the NBs-CN for 3 gained sample of comparative example, Bulk-CN
The FTIR collection of illustrative plates of conventional calcination tripolycyanamide powder body, as a result finds, when the target temperature of first stage is less than 500 DEG C, gained is produced
Some are different for thing and target product (graphite phase carbon nitride), there is not the composition of polycondensation completely in product, i.e., so-called containing miscellaneous
Matter, when target temperature is higher than 550 DEG C, polycondensation excessively causes yield to reduce.So first stage temperature is preferably above 500
DEG C, but this stage mainly allow non-polycondensation composition polycondensation again, therefore temperature can not be too high, and preferred 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 simply changed, the temperature is controlled and is less than
580 DEG C are more than 600 DEG C, and experimental result finds, when target temperature is less than 580 DEG C, ultrathin nanometer structure in final sample
Graphite phase carbon nitride percentage ratio compare embodiment 1 reduce (as shown in the FESEM of Figure 11 contrast, left figure be this comparative example product,
Product of the right figure for embodiment 1), this is likely due to, and temperature is relatively low, and ammonia there is no enough kinetic energy and enter graphite-phase
Between carbon nitride layer, it is unfavorable for peeling off；
And when temperature is more than 600 DEG C, ultra-thin graphite phase carbon nitride is almost decomposed completely, almost no target product.
Comparative example 5
It is substantially the same manner as Example 1, the temperature retention time of gradient increased temperature second stage is simply changed, test result indicate that,
When temperature retention time is less than 2h, in final sample, the graphite phase carbon nitride percentage ratio of ultrathin nanometer structure is compared embodiment 1 and is reduced (such as
Contrast shown in the FESEM of Figure 12, product of the left figure for the present embodiment, product of the right figure for embodiment 1), this is likely due to ammonia
Time of contact is shorter at high temperature with block materials for gas, and ammonia does not fully permeate graphite phase carbon nitride interlayer, similarly unfavorable
In being completely exfoliated；When temperature is more than 3h, the fragile part (such as rejected region) of part superthin section can be etched by ammonia so that
Superthin section is destroyed), increase highly energy-consuming in addition, it is uneconomical.
Comparative example 6
In embodiment 2 change process presoma nitric acid concentration, using 0.1M nitric acid treatment tripolycyanamide presoma when,
The flocculent deposit for being white is obtained, the precipitated crystal Performance comparision of the type is poor, and the nitridation toner body obtained after calcining does not gather
The composition of conjunction is on the high side, to further thinning unfavorable.
Comparative example 7
In embodiment 2 change process presoma nitric acid concentration, using 3M nitric acid treatment tripolycyanamide presoma when, by
There is strong oxidisability in relatively dense nitric acid so that forerunner's body portion starts oxidation, good super of crystallinity will be cannot get
The presoma of molecular structure.
Embodiment 2
1) presoma is processed：Tripolycyanamide solid dissolving is formed into settled solution in ethanol solution, then Deca
The salpeter solution of 0.5M, has white precipitate to produce, then by this white precipitate filtering vacuum drying for standby；
2) prepare block graphite phase carbon nitride (g-C3N4) photocatalyst material：By step 1) obtained by white depositions move
Into crucible, then crucible is positioned in Muffle furnace and 560 DEG C is warming up to the heating rate of 20 DEG C/min, and be incubated 3h, it is cold
But faint yellow solid is obtained afterwards；
3) prepare graphite phase carbon nitride (g-C3N4) photocatalyst material superfine powder：By step 2) obtained by yellowish color lump
Body graphite phase carbon nitride (g-C3N4) be placed in beaker, it is that 0.5g/ml is newborn to add a certain amount of ethanol to form concentration under stirring condition
Then the emulsion be placed in ball milling 24h in ball mill by turbid liquid, after terminating is vacuum dried gained sample；
4) prepare the ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) photocatalyst material：By step 3) in ball milling be dried after
Powder body and ammonium sulfate or ammonium chloride (mass ratio is 1:1.5) it is placed in tube furnace, passes first into argon 30min deoxygenations, so
Gradient increased temperature is set under the conditions of logical argon afterwards, first 540 DEG C is warming up to 1-5 DEG C/min heating rates, and is incubated 2h, Ran Houzai
600 DEG C are warming up to 15 DEG C/min heating rates, and are incubated 3h, the ultra-thin graphite phase carbon nitride (g- of ammonification after cooling, can be obtained
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 is presented the ultra-thin form of fold, superthin section upper surface is smooth, does not have loose structure, hole
Defect is less, similar to ultra-thin graphene-structured.Thickness is homogeneous, is 3nm-5nm.
Ultra-thin graphite phase carbon nitride (the g-C of ammonification prepared by XRD phenetic analysis description3N4) photocatalyst material spreads out
Penetrate peak basically identical with block materials, 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 the diffraction maximum of blunt and wideization, illustrate the ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) photocatalyst material exist it is unformed
The structure of state.
Infrared Characterization analytic explanation：Ultra-thin graphite phase carbon nitride (the g-C of ammonification prepared by the present embodiment3N4) photocatalyst
The absorption peak-to-peak of material is basically identical with block materials, further illustrates both basic molecular structure concordance, however, for super
Thin graphite phase carbon nitride (g-C3N4) photocatalyst material absorption collection of illustrative plates, in 3100-3400cm-1In the range of absorb and be remarkably reinforced,
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 processed：Tripolycyanamide solid dissolving is formed into settled solution in ethanol solution, then Deca
The salpeter solution of 0.5M, has white precipitate to produce, then by this white precipitate filtering vacuum drying for standby；
2) prepare block graphite phase carbon nitride (g-C3N4) photocatalyst material：By step 1) obtained by white depositions move
Into crucible, then crucible is positioned in Muffle furnace and 530 DEG C is warming up to the heating rate of 20 DEG C/min, and be incubated 4h, it is cold
But faint yellow solid is obtained afterwards；
3) prepare graphite phase carbon nitride (g-C3N4) photocatalyst material superfine powder：By step 2) obtained by yellowish color lump
Body graphite phase carbon nitride (g-C3N4) be placed in beaker, it is that 1.5g/ml is newborn to add a certain amount of ethanol to form concentration under stirring condition
Then the emulsion be placed in ball milling 20h in ball mill by turbid liquid, after terminating is vacuum dried gained sample；
4) prepare the ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) photocatalyst material：By step 3) in ball milling be dried after
Powder body and ammonium sulfate or ammonium chloride (mass ratio is 1:3) it is placed in tube furnace, passes first into argon deoxygenation, then in logical argon
Gradient increased temperature is set under gas bar part, first 510 DEG C is warming up to 1-5 DEG C/min heating rates, and is incubated 3h, then again with 15 DEG C/
Min heating rates are warming up to 560 DEG C, and are incubated 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 is presented the ultra-thin form of fold, superthin section upper surface is smooth, does not have loose structure, hole
Defect is less, similar to ultra-thin graphene-structured.Thickness is homogeneous, is 3nm-5nm.
Ultra-thin graphite phase carbon nitride (the g-C of ammonification prepared by XRD phenetic analysis description3N4) photocatalyst material spreads out
Penetrate peak basically identical with block materials, 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 the diffraction maximum of blunt and wideization, illustrate the ultra-thin graphite phase carbon nitride (g-C of ammonification3N4) photocatalyst material exist it is unformed
The structure of state.
Infrared Characterization analytic explanation：Ultra-thin graphite phase carbon nitride (the g-C of ammonification prepared by the present embodiment3N4) photocatalyst
The absorption peak-to-peak of material is basically identical with block materials, further illustrates both basic molecular structure concordance, however, for super
Thin graphite phase carbon nitride (g-C3N4) photocatalyst material absorption collection of illustrative plates, in 3100-3400cm-1In the range of absorb and be remarkably reinforced,
This partially absorbs the vibration that vibration belongs to the hydrogen bound to nitrogen of amino, illustrates surface ammonification success.
Claims (10)
1. the ultra-thin graphite phase carbon nitride photocatalyst material of a kind of ammonification, it is characterised in that：It similar to the tulle with fold,
In the gauze-like with fold, thickness is homogeneous, is 3-5nm；Material surface is smooth, containing abundant amino group.
2. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of a kind of ammonification, it is characterised in that：Including following step
Suddenly：
(1) tripolycyanamide is acidified, is obtained the tripolycyanamide supramolecular structure crystal for protonating, then in inertia shielding gas
Calcine under the conditions of atmosphere and graphite phase carbon nitride material be obtained, after Jing Homogenization Treatments obtain graphite phase carbon nitride (g-C3N4) light urges
Agent material superfine powder；
(2) the ammonia source material that graphite phase carbon nitride photocatalyst material superfine powder and thermal decomposition produce ammonia is placed in into tubular type
In stove, carry out logical noble gases deoxygenation and process, ladder calcining is then carried out under the conditions of inert protective atmosphere：500- is warming up to first
540 DEG C, 2-4h is incubated, then 560-600 DEG C is warming up to again, and is incubated 2-3h, the ultra-thin graphite-phase of ammonification after cooling, can be obtained
Carbon nitride photocatalyst material.
3. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 1, its feature
It is：In the step (2), ammonia source material and graphite phase carbon nitride powder quality ratio are 1:1-3.
4. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 1, its feature
It is：The heating rate that 500-540 DEG C is warming up in the step (2) is 1-5 DEG C/min.
5. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 1, its feature
It is：560-600 DEG C of heating rate >=15 DEG C/min is warming up in the step (2).
6. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 1, its feature
It is：It is ammonium sulfate or ammonium chloride that described thermal decomposition produces the material of ammonia.
7. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 1, its feature
It is：In the step (1), acidifying is that tripolycyanamide solid dissolving is formed in ethanol solution settled solution, uses dilute nitre
Acid treatment, obtains white precipitate insoluble matter, and then filtering vacuum is dried, and the tripolycyanamide supramolecular structure for obtaining protonating is brilliant
Body, it is standby.
8. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 1, its feature
It is：The salpeter solution concentration is 0.2-1mol/L.
9. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 1, its feature
It is：Calcining heat in the step (1) is 530-560 DEG C, and temperature retention time is 2-4h.
10. the preparation method of the ultra-thin graphite phase carbon nitride photocatalyst material of ammonification according to claim 1, its feature
It is：Described Homogenization Treatments are that the graphite phase carbon nitride that calcining is obtained is placed in beaker, are added certain under stirring condition
The ethanol of amount forms it into sticky emulsion, and the emulsion is placed in ball milling 18-24h in ball mill then, by institute after terminating
Obtain sample vacuum drying.
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