CN103145108A - Preparation method of C3N4 organic heterojunction - Google Patents
Preparation method of C3N4 organic heterojunction Download PDFInfo
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- CN103145108A CN103145108A CN2013100498328A CN201310049832A CN103145108A CN 103145108 A CN103145108 A CN 103145108A CN 2013100498328 A CN2013100498328 A CN 2013100498328A CN 201310049832 A CN201310049832 A CN 201310049832A CN 103145108 A CN103145108 A CN 103145108A
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Abstract
The invention provides a preparation method of a C3N4 organic heterojunction. The preparation method comprises the following steps: mixing one of thiourea, cyanamide, dicyanodiamine and melamine with urea to form a composite precursor; and calcining the precursor at 300-650DEG C to form two forbidden band structures coupled C3N4 in order to obtain the C3N4 organic heterojunction. The preparation method allows the homophytic C3N4 organic heterojunction having the advantages of environmental protection, high visible light photo-catalysis activity and high stability to be prepared, and has the advantages of simplicity, reliability, and easy control of the reaction process.
Description
Technical field
The present invention relates to the organic compound preparation field, be specifically related to a kind of C
3N
4The preparation method of organic heterojunction.
Background technology
Heterojunction is the key concept of semiconductor applications, is comprised of two kinds of different semiconductor monocrystals or isotropic substance monocrystal material, has a series of single semi-conductive characteristics that are different from.Along with the develop rapidly of nanotechnology, the combination of semiconductor material and nanotechnology is more and more tightr.Nano heterojunction is by the physico-chemical properties such as small-size effect, surface effects, quantum size effect, macro quanta tunnel effect and Dielectric confinement effect of nano material, compare with bulk heterojunctions and have a lot of advantages, for example: nano heterojunction can be supported much bigger current density, does not have the problems of electromigration of traditional unicircuit; Because nano material is less demanding to the lattice match degree, nano heterojunction connects more reliable, and selection is more wide in range; Nano heterojunction can build small size device.Therefore nano heterojunction obtains broad research in fields such as electron device, solar cell, photodissociation aquatic products hydrogen, biomedicine, environment remediation.
Environmental pollution is one of significant problem that affects human survival and development.Due to photocatalysis technology catalytic activity and high, the low price of stability and environmental friendliness, therefore at the environmental pollution control field, very large development space is arranged.TiO commonly used
2Photocatalyst exists quantum yield low and can not effectively utilize the shortcoming such as visible light, and that the built in field of heterojunction can suppress quantity of photogenerated charge is compound, improves quantum yield, if TiO
2Consist of heterojunction with narrow-band semiconductor, the sensibilized of narrow-band semiconductor can be expanded TiO
2The response spectrum scope, be expected to overcome TiO
2Above-mentioned shortcoming.Nano heterojunction photocatalysis material combines the advantage of nano material and heterojunction, is rapidly developed at the environmental pollution control field.TiO
2With metallic sulfide, TiO
2With metal oxide and TiO
2The successfully developments in succession such as heterojunction photocatalysis material with the precious metal formation.Yet the content that nano heterojunction is contained is far above in this, non-TiO
2Between semi-conductor, semi-conductor and carbon material can consist of the heterojunction photocatalysis material with quantity of photogenerated charge separating power.
In recent years, the related researcher has prepared the heterojunction photocatalyst with low energy gap width, as TiO
2With carbonization nitrogen (C
3N
4) heterojunction, BiOBr and carbonization nitrogen (C
3N
4) heterojunction etc.In prior art, report is generally the inorganic-organic heterojunction, and the preparation method mostly all very complicated, complex operation step, preparation condition is harsh, presoma is expensive etc., and some heterojunction is stable not in application process, be unfavorable for scale operation and application, limited its development at photocatalysis field or field of Environment Protection.
Summary of the invention
The technical problem to be solved in the present invention is to provide the C of a kind of environmental protection, high visible light catalytic activity and high stability homotype
3N
4The preparation method of organic heterojunction, the preparation method is simple and reliable, and reaction process is easy to control.
In order to solve above technical problem, the invention provides a kind of C
3N
4The preparation method of organic heterojunction comprises:
A kind of and urea in thiocarbamide, cyanamide, Dicyanodiamide, trimeric cyanamide is mixed form composite precursor;
Described precursor mixture is calcined under 300 ~ 650 ℃, obtained C
3N
4Organic heterojunction.
Preferably, also obtain tail gas after described calcining.
Preferably, described tail gas is NH
3, SO
2Or H
2S。
Preferably, also comprise described tail gas is passed in water or alkaline aqueous solution.
Preferably, described C
3N
4The productive rate of organic heterojunction is 95% ~ 100%.
Preferably, the temperature of described calcining is 500 ~ 650 ℃.
Preferably, the time of described calcining is 0.1 ~ 10h.
Preferably, in described precursor mixture, the mass ratio of a kind of and urea in thiocarbamide, cyanamide, Dicyanodiamide, trimeric cyanamide is (1 ~ 10): (1 ~ 10).
Preferably, described calcining is carried out in aerobic or oxygen-free environment.
The invention provides a kind of C
3N
4The preparation method of organic heterojunction comprises: a kind of and urea in thiocarbamide, cyanamide, Dicyanodiamide, trimeric cyanamide is mixed forming composite precursor; Described composite precursor is calcined under 300 ~ 650 ℃, obtained C
3N
4Organic heterojunction.The present invention uses urea, thiocarbamide, single cyanogen ammonia, Dicyanodiamide and trimeric cyanamide as presoma, by heating make between urea and thiocarbamide molecule, between urea and single cyanogen amino molecule, between urea and Dicyanodiamide molecule, carry out condensation polymerization between urea and melamine molecule, form polymer, but described polymer and unstable and can further resolve into C
3N
4Organic heterojunction.Due to the existence of heterojunction, the C of preparation
3N
4The visible light catalytic effect of organic heterojunction is the C for preparing with urea, thiocarbamide, single cyanogen ammonia, Dicyanodiamide and trimeric cyanamide separately
3N
41.4～3.5 times of visible light catalytic effect.
Method provided by the invention is convenient and swift, do not use poisonous and hazardous presoma in preparation process, and productive rate is high, and by reaction detection, all presoma urea, thiocarbamide, single cyanogen ammonia, Dicyanodiamide and trimeric cyanamide all can be participated in reaction and react completely.Urea and the reaction of thiocarbamide mixture can discharge a small amount of sulfurous gas, hydrogen sulfide and ammonia, produce without other pollutent; Urea and single cyanogen ammonia mixture, urea and Dicyanodiamide mixture and urea and trimeric cyanamide mixture discharge a small amount of ammonia in reaction process, produce without other pollutents.And the sulfurous gas, hydrogen sulfide and the ammonia that produce in above-mentioned reaction process can absorb by water, can be to environment.In addition preparation method's process provided by the invention simple, surpass controlledly, only need heating get final product, do not need complicated operation, be fit to large-scale production and application.
Description of drawings
The C of Fig. 1, the embodiment of the present invention 1 preparation
3N
4The XRD figure sheet of machine heterojunction;
The C of Fig. 2, the embodiment of the present invention 1 preparation
3N
4The uv-visible absorption spectra of machine heterojunction;
The C of Fig. 3, the embodiment of the present invention 1 preparation
3N
4The TEM collection of illustrative plates of machine heterojunction;
The C of Fig. 4, the embodiment of the present invention 13 preparations
3N
4The XRD figure sheet of machine heterojunction;
The C of Fig. 5, the embodiment of the present invention 13 preparations
3N
4The uv-visible absorption spectra of machine heterojunction;
The C of Fig. 6, the embodiment of the present invention 13 preparations
3N
4The TEM collection of illustrative plates of machine heterojunction;
The C of Fig. 7, the embodiment of the present invention 25 preparations
3N
4The XRD figure sheet of machine heterojunction;
The C of Fig. 8, the embodiment of the present invention 25 preparations
3N
4The uv-visible absorption spectra of machine heterojunction;
The C of Fig. 9, the embodiment of the present invention 25 preparations
3N
4The TEM collection of illustrative plates of machine heterojunction;
The C of Figure 10, the embodiment of the present invention 37 preparations
3N
4The XRD figure sheet of machine heterojunction;
The C of Figure 11, the embodiment of the present invention 37 preparations
3N
4The uv-visible absorption spectra of machine heterojunction;
The C of Figure 12, the embodiment of the present invention 37 preparations
3N
4The TEM collection of illustrative plates of machine heterojunction;
Figure 13, C provided by the invention
3N
4The structural representation of homotype heterojunction.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that the just restriction for further illustrating the features and advantages of the present invention rather than patent of the present invention being required of these descriptions.
The invention provides a kind of C
3N
4The preparation method of organic heterojunction comprises:
Urea is mixed with Dicyanodiamide mixture, urea the composite precursor calcining under 300 ~ 650 ℃ respectively that forms with single cyanogen ammonia mixture, urea with thiocarbamide mixture, urea with trimeric cyanamide, obtain product; Described product comprises C
3N
4Organic heterojunction.
According to the present invention, homotype C
3N
4Organic heterojunction refers to: two kinds of homotype C that forbidden band structure is different
3N
4, mate mutually its valence band and conduction band position, forms organic heterojunction.The C that forbidden band structure is different
3N
4Because there are potential difference in valence band and conduction band, under illumination, this potential difference drives light induced electron and hole from a kind of C
3N
4To another C
3N
4Migration has promoted separating of electronics and hole.
Calcine separately the C that urea obtains
3N
4Energy gap be 2.68eV ~ 2.78eV, calcine separately the C of thiocarbamide, single cyanogen ammonia, Dicyanodiamide or trimeric cyanamide preparation
3N
4Energy gap be 2.40eV ~ 2.56eV, the C that has urea to obtain
3N
4The C that obtains with one of thiocarbamide, single cyanogen ammonia, Dicyanodiamide or trimeric cyanamide
3N
4Energy gap different with structure.Therefore, the composite precursor that calcining urea and thiocarbamide are mixed to get, composite precursor, the urea that urea and single cyanogen ammonia are mixed to get and composite precursor, the urea that Dicyanodiamide is mixed to get mix the composite precursor that forms with trimeric cyanamide, can generate simultaneously two kinds of C that energy gap is different with structure
3N
4, these two kinds of C
3N
4Forbidden band structure mates mutually, forms homotype C
3N
4Heterojunction, the structure of described homotype heterojunction as shown in figure 13.Wherein, A is for calcining separately the C that urea obtains
3N
4, B is for calcining separately the C that thiocarbamide, cyanamide, Dicyanodiamide or trimeric cyanamide obtain
3N
4But calcine separately urea and calcine separately a kind of in cyanamide, thiocarbamide, Dicyanodiamide and trimeric cyanamide and obtain two kinds of C that the forbidden band is different
3N
4After again with its mechanically mixing, because mechanical effect can not make two kinds of C
3N
4Between produce combination closely, can form the homotype heterojunction so only have when calcining at the same time.
According to the present invention, described calcining can be carried out under aerobic or oxygen free condition, and wherein, calcining temperature is that the present invention prepares C
3N
4The key of organic heterojunction too high or too low for temperaturely all can not obtain C
3N
4Organic heterojunction, described calcining temperature is 300 ~ 650 ℃, is preferably 500 ~ 600 ℃, more preferably 550 ℃.Simultaneously, calcination time and presoma mass ratio are also at preparation C
3N
4Essential condition in the organic heterojunction process, described calcination time is preferably 0.1 ~ 10h, 1 ~ 5h more preferably, urea and thiocarbamide composite precursor most preferably are 2h; Urea and single cyanogen ammonia mixture, urea and Dicyanodiamide mixture and urea and trimeric cyanamide composite precursor most preferably are 3h.Described presoma mass ratio is 5:1 ~ 1:5,2:1 ~ 1:2 more preferably, urea and thiocarbamide mixture and urea and trimeric cyanamide composite precursor are most preferably all 1:1 respectively, and urea and single cyanogen ammonia mixture and urea and Dicyanodiamide composite precursor are most preferably all 2:1 respectively.Owing to not adding any other raw material, all urea and thiocarbamide composite precursor, urea and single cyanogen ammonia composite precursor, urea and Dicyanodiamide composite precursor, urea and trimeric cyanamide composite precursor can obtain C
3N
4So organic heterojunction is the C of preparation method provided by the invention preparation
3N
4The productive rate of organic heterojunction is 95% ~ 100%.
Owing to containing S element and N element in thiocarbamide, may have a small amount of SO in product
2, H
2S and NH
3Contain the N element in single cyanogen ammonia, Dicyanodiamide, trimeric cyanamide and urea, so after reaction finishes, may have a small amount of NH in product
3NH wherein
3Content maximum, described gas is passed in large water gaging or alkaline aqueous solution, make SO
2, H
2S and NH
3The ammoniacal liquor reaction that forms, thus reach the purpose of removing Tail Gas.
The C of the present invention's preparation
3N
4Organic heterojunction has laminate structure, and energy gap is 2.3 ~ 2.8eV, can significantly absorb visible light, and its absorbing wavelength red shift has excellent visible light catalytic performance to 700nm.The C that different presomas obtain under identical heat-treat condition
3N
4Have different energy gaps and structure, homotype C
3N
4The different C of forbidden band structure in organic heterojunction
3N
4Because there are potential difference in valence band and conduction band, under illumination, this potential difference drives light induced electron and hole from a kind of C
3N
4To another C
3N
4Migration has promoted separating (as shown in figure 13) of electronics and hole, is conducive to the raising of photocatalysis performance.In addition, C
3N
4Organic heterojunction has abundant avtive spot and specific surface area, therefore, under the identical condition of experiment condition, C
3N
4Organic heterojunction visible light catalytic effect is the C for preparing with urea, thiocarbamide, single cyanogen ammonia, Dicyanodiamide and trimeric cyanamide separately
3N
41.4～3.5 times of visible light catalytic effect.In addition, the C of the present invention's preparation
3N
4Effect stability in the use procedure of organic heterojunction is without deactivation phenomenom.
Compared with prior art, the present invention need not hypertoxic raw material take cheap, nontoxic urea, thiocarbamide, single cyanogen ammonia, Dicyanodiamide and trimeric cyanamide as raw material, prepares C
3N
4Organic heterojunction.Simultaneously, the method technique is simple, and cost of material is cheap, has reduced production cost, is easy to realize industrial applications.
The visible light catalyst of the present invention's preparation not only can be used for water pollution control, and in the aspects such as air pollution treatment, photolysis water hydrogen, solar cell and catalytic carrier, very large application potential is arranged also.
Be below specific embodiment provided by the invention, the chemical reagent that wherein adopts is commercial.
Embodiment 1
The mixture that takes 6.0g urea and 6.0g thiocarbamide is placed in crucible, and cover lid is calcined under aerobic conditions, and calcining temperature is 550 ℃, and calcination time is 2h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
As shown in Figure 1, the C for preparing for the invention process
3N
4The XRD figure sheet of organic heterojunction shows the C of preparation
3N
4Organic heterojunction has the graphite-phase crystal formation.
As shown in Figure 2, the C for preparing for the invention process
3N
4The uv-visible absorption spectra of organic heterojunction shows the C of preparation
3N
4Organic heterojunction can absorb visible light, and maximum absorption wavelength is 700nm.
As shown in Figure 3, the C for preparing for the invention process
3N
4The TEM collection of illustrative plates of organic heterojunction shows the C of preparation
3N
4Organic heterojunction has laminate structure.
Embodiment 2
Take 6.0g urea and the 6.0g thiocarbamide is placed in crucible, calcine under aerobic conditions, calcining temperature is 500 ℃, calcination time 4h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
Embodiment 3
Take 6.0g urea and the 6.0g thiocarbamide is placed in crucible, calcine under oxygen free condition, calcining temperature is 600 ℃, calcination time 1h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
Embodiment 4
Take 6.0g urea and the 6.0g thiocarbamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 400 ℃, and calcination time is 6h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 5
Take 6.0g urea and the 6.0g thiocarbamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 600 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 6
Take 6.0g urea and the 6.0g thiocarbamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 450 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 7
Take 6.0g urea and the 6.0g thiocarbamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 500 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 8
Take 6.0g urea and the 6.0g thiocarbamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 450 ℃, and calcination time is 4h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 9
Take 8.0g urea and the 4.0g thiocarbamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Take 4.0g urea and the 8.0g thiocarbamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 11
Take 10.0g urea and the 2.0g thiocarbamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 550 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 12
Take 2.0g urea and the 10.0g thiocarbamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 550 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
The visible light catalyst that respectively embodiment 1～12 is prepared carries out active testing, and target contaminant is Typical Air Pollution thing NO.
Experiment condition is as follows: the present invention is with the C that obtains
3N
4The organic heterojunction photocatalyst is used for the removal to NO, and detailed process is as follows: be 60% in relative humidity, oxygen content is under 21% condition, the 0.2gC that embodiment 1 is obtained
3N
4The organic heterojunction photocatalyst is placed in the NO Continuous Flow, and the starting point concentration of NO is 650ppb, and gas flow is 2.4L/min, adopts the halogen tungsten lamp of 100W, and adopts the edge filter filtering ultraviolet light of 400nm, and visible light is seen through C
3N
4The organic heterojunction photocatalyst shines, and the highest clearance that obtains NO is 40.6%, and result is as shown in table 1, and table 1 is the C that the embodiment of the present invention and comparative example obtain
3N
4The catalytic performance result of organic heterojunction photocatalyst, as can be seen from Table 1, the C of the present embodiment preparation
3N
4The organic heterojunction photocatalyst has higher clearance, C to NO under the irradiation of visible light
3N
4The visible light catalysis activity of organic heterojunction all is significantly higher than the C of single presoma preparation under identical heat-treat condition
3N
4, illustrate that it has higher visible light catalysis activity.The results of property of the visible light catalyst that table 1 embodiment 1～12 prepares.
Embodiment 13
The mixture that takes 6.0g urea and 6.0g trimeric cyanamide is placed in crucible, and cover lid is calcined under aerobic conditions, and calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
As shown in Figure 4, the C for preparing for the invention process
3N
4The XRD figure sheet of organic heterojunction shows the C of preparation
3N
4Organic heterojunction has the graphite-phase crystal formation.
As shown in Figure 5, the C for preparing for the invention process
3N
4The uv-visible absorption spectra of organic heterojunction shows the C of preparation
3N
4Organic heterojunction can absorb visible light, and maximum absorption wavelength is 700nm.
As shown in Figure 6, the C for preparing for the invention process
3N
4The TEM collection of illustrative plates of organic heterojunction shows the C of preparation
3N
4Organic heterojunction has laminate structure.
Embodiment 14
Take 6.0g urea and the 6.0g trimeric cyanamide is placed in crucible, calcine under aerobic conditions, calcining temperature is 500 ℃, calcination time 4h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
Embodiment 15
Take 6.0g urea and the 6.0g trimeric cyanamide is placed in crucible, calcine under oxygen free condition, calcining temperature is 600 ℃, calcination time 1h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
Embodiment 16
Take 6.0g urea and the 6.0g trimeric cyanamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 400 ℃, and calcination time is 6h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 17
Take 6.0g urea and the 6.0g trimeric cyanamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 600 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 18
Take 6.0g urea and the 6.0g trimeric cyanamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 450 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 19
Take 6.0g urea and the 6.0g trimeric cyanamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 500 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Take 6.0g urea and the 6.0g trimeric cyanamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 450 ℃, and calcination time is 4h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 21
Take 4.0g urea and the 8.0g trimeric cyanamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 22
Take 8.0g urea and the 4.0g trimeric cyanamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 23
Take 10.0g urea and the 2.0g trimeric cyanamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 24
Take 2.0g urea and the 10.0g trimeric cyanamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
The visible light catalyst that respectively embodiment 1～12 is prepared carries out active testing, and target contaminant is Typical Air Pollution thing NO.
Experiment condition is as follows: the present invention is with the C that obtains
3N
4The organic heterojunction photocatalyst is used for the removal to NO, and detailed process is as follows: be 60% in relative humidity, oxygen content is under 21% condition, the 0.2gC that embodiment 1 is obtained
3N
4The organic heterojunction photocatalyst is placed in the NO Continuous Flow, and the starting point concentration of NO is 650ppb, and gas flow is 2.4L/min, adopts the halogen tungsten lamp of 100W, and adopts the edge filter filtering ultraviolet light of 400nm, and visible light is seen through C
3N
4The organic heterojunction photocatalyst shines, and the highest clearance that obtains NO is 41.3%, and result is as shown in table 2, and table 2 is the C that the embodiment of the present invention and comparative example obtain
3N
4The catalytic performance result of organic heterojunction photocatalyst, as can be seen from Table 2, the C of the present embodiment preparation
3N
4The organic heterojunction photocatalyst has higher clearance, C to NO under the irradiation of visible light
3N
4The visible light catalysis activity of organic heterojunction all is significantly higher than the C of single presoma preparation under identical heat-treat condition
3N
4, illustrate that it has higher visible light catalysis activity.The results of property of the visible light catalyst that table 2 embodiment 1～12 prepares.
The results of property of the visible light catalyst that table 2 embodiment 1～12 prepares
Embodiment 25
The mixture that takes the single cyanogen ammonia of 6.0g urea and 6.0g is placed in crucible, and cover lid is calcined under aerobic conditions, and calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
As shown in Figure 7, the C for preparing for the invention process
3N
4The XRD figure sheet of organic heterojunction shows the C of preparation
3N
4Organic heterojunction has the graphite-phase crystal formation.
As shown in Figure 8, the C for preparing for the invention process
3N
4The uv-visible absorption spectra of organic heterojunction shows the C of preparation
3N
4Organic heterojunction can absorb visible light, and maximum absorption wavelength is 700nm.
As shown in Figure 9, the C for preparing for the invention process
3N
4The TEM collection of illustrative plates of organic heterojunction shows the C of preparation
3N
4Organic heterojunction has laminate structure.
Embodiment 26
Take the single cyanogen ammonia of 6.0g urea and 6.0g and be placed in crucible, calcine under aerobic conditions, calcining temperature is 500 ℃, calcination time 4h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
Embodiment 27
Take the single cyanogen ammonia of 6.0g urea and 6.0g and be placed in crucible, calcine under oxygen free condition, calcining temperature is 600 ℃, calcination time 1h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
Embodiment 28
Take the single cyanogen ammonia of 6.0g urea and 6.0g and be placed in crucible, then calcine under oxygen free condition, calcining temperature is 400 ℃, and calcination time is 6h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 29
Take the single cyanogen ammonia of 6.0g urea and 6.0g and be placed in crucible, then calcine under aerobic conditions, calcining temperature is 600 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Take the single cyanogen ammonia of 6.0g urea and 6.0g and be placed in crucible, then calcine under aerobic conditions, calcining temperature is 450 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 31
Take the single cyanogen ammonia of 6.0g urea and 6.0g and be placed in crucible, then calcine under oxygen free condition, calcining temperature is 500 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 32
Take the single cyanogen ammonia of 6.0g urea and 6.0g and be placed in crucible, then calcine under oxygen free condition, calcining temperature is 450 ℃, and calcination time is 4h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 33
Take the single cyanogen ammonia of 4.0g urea and 8.0g and be placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 34
Take the single cyanogen ammonia of 8.0g urea and 4.0g and be placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 35
Take the single cyanogen ammonia of 10.0g urea and 2.0g and be placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 36
Take the single cyanogen ammonia of 2.0g urea and 10.0g and be placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
The visible light catalyst that respectively embodiment 1～12 is prepared carries out active testing, and target contaminant is Typical Air Pollution thing NO.
Experiment condition is as follows: the present invention is with the C that obtains
3N
4The organic heterojunction photocatalyst is used for the removal to NO, and detailed process is as follows: be 60% in relative humidity, oxygen content is under 21% condition, the 0.2gC that embodiment 1 is obtained
3N
4The organic heterojunction photocatalyst is placed in the NO Continuous Flow, and the starting point concentration of NO is 650ppb, and gas flow is 2.4L/min, adopts the halogen tungsten lamp of 100W, and adopts the edge filter filtering ultraviolet light of 400nm, and visible light is seen through C
3N
4The organic heterojunction photocatalyst shines, and the highest clearance that obtains NO is 39.7%, and result is as shown in table 3, and table 3 is the C that the embodiment of the present invention and comparative example obtain
3N
4The catalytic performance result of organic heterojunction photocatalyst, as can be seen from Table 3, the C of the present embodiment preparation
3N
4The organic heterojunction photocatalyst has higher clearance, C to NO under the irradiation of visible light
3N
4The visible light catalysis activity of organic heterojunction all is significantly higher than the C of single presoma preparation under identical heat-treat condition
3N
4, illustrate that it has higher visible light catalysis activity.The results of property of the visible light catalyst that table 3 embodiment 1～12 prepares.
The results of property of the visible light catalyst that table 3 embodiment 25～36 prepares
Embodiment 37
The mixture that takes 6.0g urea and 6.0g Dicyanodiamide is placed in crucible, and cover lid is calcined under aerobic conditions, and calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
As shown in figure 10, the C for preparing for the invention process
3N
4The XRD figure sheet of organic heterojunction shows the C of preparation
3N
4Organic heterojunction has the graphite-phase crystal formation.
As shown in figure 11, the C for preparing for the invention process
3N
4The uv-visible absorption spectra of organic heterojunction shows the C of preparation
3N
4Organic heterojunction can absorb visible light, and maximum absorption wavelength is 700nm.
As shown in figure 12, the C for preparing for the invention process
3N
4The TEM collection of illustrative plates of organic heterojunction shows the C of preparation
3N
4Has laminate structure.
Embodiment 38
Take 6.0g urea and the 6.0g Dicyanodiamide is placed in crucible, calcine under aerobic conditions, calcining temperature is 500 ℃, calcination time 4h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
Embodiment 39
Take 6.0g urea and the 6.0g Dicyanodiamide is placed in crucible, calcine under oxygen free condition, calcining temperature is 600 ℃, calcination time 1h, the cooling C that obtains
3N
4The organic heterojunction catalyzer.
Take 6.0g urea and the 6.0g Dicyanodiamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 400 ℃, and calcination time is 6h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 41
Take 6.0g urea and the 6.0g Dicyanodiamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 600 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 42
Take 6.0g urea and the 6.0g Dicyanodiamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 450 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 43
Take 6.0g urea and the 6.0g Dicyanodiamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 500 ℃, and calcination time is 2h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 44
Take 6.0g urea and the 6.0g Dicyanodiamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 450 ℃, and calcination time is 4h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 45
Take 8.0g urea and the 4.0g Dicyanodiamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 46
Take 4.0g urea and the 8.0g Dicyanodiamide is placed in crucible, then calcine under aerobic conditions, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 47
Take 10.0g urea and the 2.0g Dicyanodiamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction.
Embodiment 48
Take 2.0g urea and the 10.0g Dicyanodiamide is placed in crucible, then calcine under oxygen free condition, calcining temperature is 550 ℃, and calcination time is 3h, the cooling C that obtains
3N
4Organic heterojunction;
The visible light catalyst that respectively embodiment 1～12 is prepared carries out active testing, and target contaminant is Typical Air Pollution thing NO.
Experiment condition is as follows: the present invention is with the C that obtains
3N
4The organic heterojunction photocatalyst is used for the removal to NO, and detailed process is as follows: be 60% in relative humidity, oxygen content is under 21% condition, the 0.2gC that embodiment 1 is obtained
3N
4The organic heterojunction photocatalyst is placed in the NO Continuous Flow, and the starting point concentration of NO is 650ppb, and gas flow is 2.4L/min, adopts the halogen tungsten lamp of 100W, and adopts the edge filter filtering ultraviolet light of 400nm, and visible light is seen through C
3N
4The organic heterojunction photocatalyst shines, and the maximum material removal rate that obtains NO is 40.8%, and result is as shown in table 1, and table 4 is the C that the embodiment of the present invention and comparative example obtain
3N
4The catalytic performance result of organic heterojunction photocatalyst, as can be seen from Table 4, the C of the present embodiment preparation
3N
4The organic heterojunction photocatalyst has higher clearance, C to NO under the irradiation of visible light
3N
4The visible light catalysis activity of organic heterojunction all is significantly higher than the C of single presoma preparation under identical heat-treat condition
3N
4, illustrate that it has higher visible light catalysis activity.
The results of property of the visible light catalyst that table 4 embodiment 37～48 prepares.
Comparative example 1:
Calcining urea, obtain a kind of C separately
3N
4(being labeled as A) calcined separately one of thiocarbamide, single cyanogen ammonia, Dicyanodiamide or trimeric cyanamide and obtained another C
3N
4(being labeled as B) carries out mechanically mixing with A and B according to certain ratio, obtains the C that A and B mix
3N
4Mixture.Under same light catalysis test condition, to above-mentioned C
3N
4Mixture carries out active testing, and result shows, C
3N
4Mixture is 18.1% ~ 24.4% to the clearance of NO, lower than the C of the present invention's preparation
3N
4Organic heterojunction.This shows that A and B are carried out mechanically mixing can not obtain C
3N
4Heterojunction, C
3N
4Therefore the photocatalytic activity of mixture can not be enhanced.Obviously, the composite precursor that adopts the present invention to describe is preparation C
3N
4The prerequisite of organic heterojunction.
Above to a kind of C provided by the invention
3N
4The preparation method of organic heterojunction is described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (9)
1. C
3N
4The preparation method of organic heterojunction is characterized in that, comprising:
A kind of and urea in thiocarbamide, cyanamide, Dicyanodiamide, trimeric cyanamide is mixed form precursor mixture;
Described precursor mixture is calcined under 300 ~ 650 ℃, obtained C
3N
4Organic heterojunction.
2. preparation method according to claim 1, is characterized in that, also obtains tail gas after calcining.
3. preparation method according to claim 2, is characterized in that, described tail gas is NH
3, SO
2Or H
2S。
4. preparation method according to claim 2, is characterized in that, also comprises described tail gas is passed in water or alkaline aqueous solution.
5. preparation method according to claim 1, is characterized in that, described C
3N
4The productive rate of organic heterojunction is 95% ~ 100%.
6. preparation method according to claim 1, is characterized in that, the temperature of described calcining is 500 ~ 650 ℃.
7. preparation method according to claim 1, is characterized in that, the time of described calcining is 0.1 ~ 10h.
8. preparation method according to claim 1, is characterized in that, the mass ratio of a kind of and urea in described precursor mixture in thiocarbamide, cyanamide, Dicyanodiamide, trimeric cyanamide is (1 ~ 10): (1 ~ 10).
9. preparation method according to claim 1, is characterized in that, described calcining is carried out in aerobic or oxygen-free environment.
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