CN103301867B - Carbon nitride photocatalyst of a kind of inorganic ions doping and preparation method thereof - Google Patents

Carbon nitride photocatalyst of a kind of inorganic ions doping and preparation method thereof Download PDF

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CN103301867B
CN103301867B CN201310256950.6A CN201310256950A CN103301867B CN 103301867 B CN103301867 B CN 103301867B CN 201310256950 A CN201310256950 A CN 201310256950A CN 103301867 B CN103301867 B CN 103301867B
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carbon nitride
nitride photocatalyst
doping
present
inorganic ions
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CN103301867A (en
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董帆
李秋燕
王震宇
孙艳娟
赵再望
傅敏
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CHONGQING TRANSSUT TECHNOLOGY Co.,Ltd.
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Chongqing Technology and Business University
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Abstract

The invention provides a kind of inorganic ions doping carbon nitride photocatalyst and preparation method thereof, there is the molecular formula shown in formula (I).Its preparation method is: carbon nitrogen source is fully mixed post-drying in aqueous with inorganic salts, calcines, and obtains the carbon nitride photocatalyst of the inorganic ions doping with the molecular formula shown in formula (I).In photochemical catalyst provided by the invention, inorganic ions enters into C 3n 4lattice in or in interbed, the doping of inorganic ions makes C provided by the invention 3n 4photochemical catalyst visible light catalysis activity significantly strengthens.Experiment shows, the inorganic ions doping C with two-dimensional structure provided by the invention 3n 4the visible light catalysis activity of photochemical catalyst is the C that do not adulterate 3n 41.5 ~ 3 times of photochemical catalyst.In addition, preparation method's mild condition provided by the invention, simple to operate, be beneficial to its large-scale production.

Description

Carbon nitride photocatalyst of a kind of inorganic ions doping and preparation method thereof
Technical field
The present invention relates to light-catalysed technical field, particularly relate to carbon nitride photocatalyst of a kind of inorganic ions doping and preparation method thereof.
Background technology
Current, how facing mankind environmental pollution and the large basic problem of energy shortage two, effectively utilize continuable clean solar energy to solve environmental problem and energy problem is more and more subject to global concern and attention.In recent years, along with the development of photocatalysis technology, realize photocatalysis technology by solar energy and to be converted in chemical energy field in environmental pollution purification and solar energy and to show huge application potential.
What play an important role in photocatalytic process is catalysis material.Because the photochemical catalyst of visible ray optical drive directly can utilize sunshine or people's irradiation, and show huge application potential at environmental protection, material science and solar energy converting field.The parent that the photochemical catalyst therefore with visible light activity is more and more subject to researcher looks at.In the past few decades, scientists endeavours the photochemical catalyst with research and development with visible light activity always, such as inorganic visible light catalyst Fe 2o 3, (BiO) 2cO 3, MoS 2, SrTiO 3and WO 3/ BiOCl, organic visible light catalyst g-C 3n 4, simple substance photochemical catalyst Si, P, S and Se.Particularly class Graphene carbonitride (g-C 3n 4), it is the first the organic photochemical catalyst found up to now, it have suitable energy gap (about 2.7eV), high heat endurance and chemical stability, nontoxic, bio-compatibility, with low cost, be easy to the advantages such as chemical modification, receive the extensive concern of researcher.
In the research to semiconductor type photochemical catalyst, class Graphene carbonitride semi-conducting material has unique electronic structure, and excellent light absorpting ability and higher photocatalysis performance, what it obtained researches and develops more widely.But, because carbonitride specific area is lower, the easy recombination rate of photo-generate electron-hole is high and there is the shortcomings such as a large amount of faults of construction, make carbonitride activity under visible light not ideal enough, limit the large-scale application of carbonitride.Therefore, be necessary to develop the modification of effective method for carbonitride, to improve its photocatalysis performance further.
Summary of the invention
Carbon nitride photocatalyst that the object of the present invention is to provide a kind of inorganic ions to adulterate and preparation method thereof, the carbon nitride photocatalyst of described inorganic ion doping can strengthen visible absorption, improve the separative efficiency of light induced electron, there is higher visible light catalysis activity.
The invention provides the carbon nitride photocatalyst of a kind of inorganic ions doping, there is the molecular formula shown in formula (I):
[X] m[C 3N 4] (1-m)（I）；
Wherein, m is 1% ~ 40%.
Preferably, described m is 2% ~ 20%.
Preferred X is KCl, KBr, KI, NH 4cl, NH 4br, NH 4i, KNO 3, K 2sO 4, K 2cO 3, KH 2pO 4, CaCl 2, MgCl 2, BaCl 2, (NH 4) 2sO 4, NH 4nO 3, (NH 4) 2cO 3.
Preferred carbonitride raw material is single cyanogen ammonia, dicyan diamino, melamine, cyanuric acid, thiocarbamide or urea.
The invention provides inorganic ions doping carbon nitride photocatalyst and preparation method thereof, comprise the following steps:
Carbon nitrogen source and inorganic salts are fully mixed post-drying in aqueous, calcine, obtain the carbon nitride photocatalyst of the inorganic ions doping with molecular formula shown in formula (I):
[X] m[C 3N 4] (1-m)（I）；
Wherein, m is 1% ~ 40%.
Preferably, described carbon nitrogen source is single cyanogen ammonia, dicyan diamino, melamine, cyanuric acid, thiocarbamide or urea.
Preferably, described inorganic salts are KCl, KBr, KI, NH 4cl, NH 4br, NH 4i, KNO 3, K 2sO 4, K 2cO 3, KH 2pO 4, CaCl 2, MgCl 2, BaCl 2, (NH 4) 2sO 4, NH 4nO 3or (NH 4) 2cO 3.
Preferably, the mass ratio of described carbon nitrogen source and described inorganic salts is 1:(0.01 ~ 0.4).
Preferably, the mass ratio of described carbon nitrogen source and described inorganic salts is 1:(0.02 ~ 0.2).
Preferably, described bake out temperature is 40 ~ 70 DEG C.
Preferably, described calcining heat is 400 ~ 650 DEG C.
Preferably, described calcination time is 0.5 ~ 10h.
The invention provides carbon nitride photocatalyst of a kind of inorganic ions doping and preparation method thereof, the carbon nitride photocatalyst of inorganic ions doping provided by the invention has the molecular formula shown in formula (I): [X] m[C 3n 4] (1-m)(I); Wherein, m is 1% ~ 40%.Both for raw material with carbon nitrogen source and inorganic salts, are fully mixed post-drying, calcine by the present invention in aqueous, obtain the carbon nitride photocatalyst of the inorganic ions doping with the molecular formula shown in formula (I).In preparation process, described inorganic salts are all dissociated into ion under aqueous conditions, presoma is in carbonitride process in high temperature polymerization, the in-situ doped structure entering into carbonitride of inorganic ions, obtains the carbon nitride photocatalyst of the inorganic ions doping with molecular formula shown in formula (I).The inorganic ions of doping and C 3n 4form chemical bond, change C 3n 4forbidden band structure.C 3n 4in structure, mixing of inorganic ions makes the energy gap of inorganic ions provided by the invention doping carbon nitride photocatalyst be decreased to 2.2eV ~ 2.6eV, promoting catalyst is to the absorption of visible ray, the separative efficiency in light induced electron and hole is enhanced simultaneously, and the carbon nitride photocatalyst of therefore inorganic ions doping has higher visible light catalysis activity.Experimental result shows, the carbon nitride photocatalyst of inorganic ions doping provided by the invention is under the irradiation of visible ray, be 30% ~ 50% to the clearance of NO, substantially increase the removal to NO under the condition of visible ray, be conducive to its application in environment and energy field.
In addition, method provided by the invention does not need to use template, can obtain the carbon nitride photocatalyst of inorganic ions doping under mild conditions, and equipment is simple to operation, can be used for large-scale production.
Accompanying drawing explanation
Fig. 1 is the UV-visDRS collection of illustrative plates of the carbon nitride photocatalyst of potassium chloride doping prepared by the embodiment of the present invention 1;
Fig. 2 is the PL collection of illustrative plates of the carbon nitride photocatalyst of potassium chloride doping prepared by the embodiment of the present invention 1;
Fig. 3 is the SEM photo of the carbon nitride photocatalyst of KBr doping prepared by the embodiment of the present invention 2;
Fig. 4 is the UV-visDRS collection of illustrative plates of the carbon nitride photocatalyst of KI doping prepared by the embodiment of the present invention 3;
Fig. 5 is the XRD collection of illustrative plates of the carbon nitride photocatalyst of ammonium chloride doping prepared by the embodiment of the present invention 4;
Fig. 6 is the XRD collection of illustrative plates of the carbon nitride photocatalyst of ammonium bromide doping prepared by the embodiment of the present invention 5;
Fig. 7 is the NO clearance figure of the carbon nitride photocatalyst of ammonium iodide doping prepared by the embodiment of the present invention 6;
Fig. 8 is the TEM photo of the carbon nitride photocatalyst of potassium nitrate doping prepared by the embodiment of the present invention 7;
Fig. 9 is the energy spectrogram of the carbon nitride photocatalyst of potassium nitrate doping prepared by the embodiment of the present invention 7;
Figure 10 is the TEM photo of the carbon nitride photocatalyst of potassium sulfate doping prepared by the embodiment of the present invention 8;
Figure 11 is the energy spectrogram of the carbon nitride photocatalyst of potassium sulfate doping prepared by the embodiment of the present invention 8;
Figure 12 is the XRD collection of illustrative plates of the carbon nitride photocatalyst of potash doping prepared by the embodiment of the present invention 9;
Figure 13 is the UV-vis DRS collection of illustrative plates of the carbon nitride photocatalyst of potassium dihydrogen phosphate doping prepared by the embodiment of the present invention 10;
Figure 14 is the SEM photo of the carbon nitride photocatalyst of barium chloride doping prepared by the embodiment of the present invention 11;
Figure 15 is the UV-visDRS collection of illustrative plates of the carbon nitride photocatalyst of calcium chloride doping prepared by the embodiment of the present invention 12;
Figure 16 is the NO clearance figure of the carbon nitride photocatalyst of magnesium chloride doping prepared by the embodiment of the present invention 13;
Figure 17 is the NO clearance figure of the carbon nitride photocatalyst of ammonium sulfate doping prepared by the embodiment of the present invention 14;
Figure 18 is the NO clearance figure of the carbon nitride photocatalyst of ammonium nitrate doping prepared by the embodiment of the present invention 15;
Figure 19 is the PL collection of illustrative plates of the carbon nitride photocatalyst of ammonium nitrate doping prepared by the embodiment of the present invention 15;
Figure 20 is the NO clearance figure of the carbon nitride photocatalyst of ammonium carbonate doping prepared by the embodiment of the present invention 16.
Detailed description of the invention
The invention provides carbon nitride photocatalyst of a kind of inorganic ions doping and preparation method thereof, there is the molecular formula shown in formula (I):
[X] m[C 3N 4] (1-m)（I）；
Wherein, m is 1% ~ 40%.
In inorganic ions doping carbon nitride photocatalyst provided by the invention, inorganic ions enters into described C 3n 4in structure, obtain the inorganic ions doping carbon nitride photocatalyst with molecular formula shown in formula (I), wherein m is 1% ~ 40%, is preferably 2% ~ 20%, is more preferably 5% ~ 15%.
The carbon nitride photocatalyst of inorganic ions doping provided by the invention, due to C 3n 4in structure, the existence of inorganic ions makes its energy gap be decreased to 2.2eV ~ 2.6eV, and visible absorption strengthens, and the separative efficiency in light induced electron and hole is improved simultaneously, and the carbonitride of therefore inorganic ions doping shows higher visible light catalysis activity.Experimental result shows, inorganic ions doping carbon nitride photocatalyst provided by the invention is under the irradiation of visible ray, be 30% ~ 50% to the clearance of NO, substantially increase the removal efficiency to NO under the condition of visible ray, illustrate that inorganic ions provided by the invention doping carbon nitride photocatalyst has higher visible light catalysis activity.
The invention provides the preparation method of the carbon nitride photocatalyst of a kind of inorganic ions doping, comprise the following steps:
Carbon nitrogen source and inorganic salts are fully mixed post-drying in aqueous, calcine, obtain the carbon nitride photocatalyst of the inorganic ions doping with molecular formula shown in formula (I):
[X] m[C 3N 4] (1-m)（I）；
Wherein, m is 1% ~ 40%, is preferably 2% ~ 20%, is more preferably 5% ~ 15%;
Described carbon nitrogen source is the raw material preparing carbonitride, is preferably single cyanogen ammonia, dicyanodiamine, melamine, cyanuric acid, thiocarbamide or urea;
Described inorganic salts be potassium chloride, KBr, KI, ammonium chloride, ammonium bromide, ammonium iodide, potassium nitrate, potassium sulfate, potash, potassium dihydrogen phosphate, calcium chloride, magnesium chloride, barium chloride, ammonium sulfate, ammonium nitrate or carbonic acid by.
The present invention first by carbon nitrogen source and inorganic salts soluble in water, the mixed solution obtained is dried at low temperatures; Described carbon nitrogen source is preferably single cyanogen ammonia, dicyanodiamine, melamine, cyanuric acid, thiocarbamide or urea.Described inorganic salts are preferably potassium chloride, KBr, KI, ammonium chloride, ammonium bromide, ammonium iodide, potassium nitrate, potassium sulfate, potash, potassium dihydrogen phosphate, calcium chloride, magnesium chloride, barium chloride, ammonium sulfate, ammonium nitrate or carbonic acid and press; Described water is preferably deionized water; The mass ratio of described carbonitride and described inorganic salts is preferably 1:(0.01 ~ 0.4), be more preferably 1:(0.02 ~ 0.2).First the present invention preferably prepares inorganic salt solution, and then in the aqueous solution of described inorganic salts, add carbon nitrogen source, the temperature obtaining drying described in mixed solution post-drying is preferably 40 ~ 70 DEG C.
The present invention by after oven dry under described mixed solution low temperature, then carries out roasting to mixture, obtains the carbon nitride photocatalyst of the inorganic ions doping with molecular formula shown in formula (I).In the present invention, described inorganic salts are all dissociated into ion in aqueous; Meanwhile, in the process of described calcination, described inorganic ions enters into carbonitride layer structure, thus obtains the carbon nitride photocatalyst of the inorganic ions doping with molecular formula shown in formula (I).In inorganic ions doping carbon nitride photocatalyst provided by the invention, inorganic ions enters into the layer structure of carbonitride, thus make the energy gap of the inorganic ions doping carbon nitride photocatalyst obtained be decreased to 2.2eV ~ 2.6eV, its absorption spectrum is widened to visible region from ultraviolet spectra district, therefore, it is possible to absorb visible ray.In the present invention, the temperature of described calcination is preferably 400 DEG C ~ 650 DEG C, is more preferably 480 DEG C ~ 600 DEG C; The time of described calcination is preferably 0.5 hour ~ 10 hours, is more preferably 1 hour ~ 5 hours.
After calcination completes, reaction system preferably cools by the present invention, obtains product.The present invention, to the parameter of described cooling, adopts the technical scheme of cooling well known to those skilled in the art.
After obtaining product, described product is preferably milled by the present invention, obtains powder-product.The present invention does not have special restriction to described parameter of milling, and adopts technical scheme of milling well known to those skilled in the art.
After obtaining having the inorganic ions doping carbon nitride photocatalyst of molecular formula shown in formula (I), the carbon nitride photocatalyst of the present invention to the inorganic ions doping obtained characterizes and performance test, detailed process and result as follows:
The carbon nitride photocatalyst of the present invention to the inorganic ions doping obtained carries out X-ray diffraction (XRD) analysis, and result shows, and the thing of inorganic ions doping carbon nitride photocatalyst provided by the invention is C mutually 3n 4.
The present invention carries out UV-vis DRS (UV-vis DRS) analysis to the inorganic ions doping carbon nitride photocatalyst obtained, result shows, the broadband, forbidden band with the inorganic ions doping carbon nitride photocatalyst of molecular formula shown in formula (I) provided by the invention is 2.2eV ~ 2.6eV, thus make its absorption spectrum generation red shift, therefore it can absorb more visible ray.
The carbon nitride photocatalyst of the present invention to the inorganic ions doping obtained carries out ESEM (SEM) analysis, and result shows, and the carbon nitride photocatalyst of inorganic ions doping provided by the invention has the nanometer sheet structure of stratiform.
The present invention carries out projection Electronic Speculum (TEM) analysis to the inorganic ions doping carbon nitride photocatalyst obtained, and result shows, and the carbon nitride photocatalyst of inorganic ions doping provided by the invention has the nanometer sheet structure of stratiform.
The catalytic performance of carbon nitride photocatalyst of the present invention to the inorganic ions doping obtained is tested, detailed process and result as follows:
40% ~ 80% is preferably in relative humidity, oxygen content is under the condition of 15% ~ 25%, preferably inorganic ions doping carbon nitride photocatalyst provided by the invention for 0.1g ~ 0.5g is placed in NO Continuous Flow, the initial concentration of described NO is preferably 500ppb ~ 650ppb, the gas flow of described NO Continuous Flow is preferably 2.4L/min ~ 4.0L/mim, adopt the halogen tungsten lamp of 100W, and with the edge filter filtering ultraviolet light of 420nm, make edge filter described in visible light-transmissive, thus visible ray is irradiated described inorganic ions doping carbon nitride photocatalyst, obtain its clearance to NO.Experimental result shows, inorganic ions doping carbon nitride photocatalyst provided by the invention is under the irradiation of visible ray, be 30% ~ 50% to the clearance of NO, this illustrates that inorganic ions provided by the invention doping carbon nitride photocatalyst has higher visible light catalysis activity, and higher than the visible light catalysis activity of independent carbon nitride photocatalyst.
The invention provides a kind of inorganic ions doping carbon nitride photocatalyst and preparation method thereof, inorganic ions doping carbon nitride photocatalyst provided by the invention has the molecular formula shown in formula (I): [X] m[C 3n 4] (1-m)(I); Wherein, m is 1% ~ 40%.The present invention is to prepare the raw material of carbonitride and inorganic salts for raw material, dry under it being mixed in aqueous rear low temperature, finally carry out calcination, the inorganic ions obtaining having molecular formula shown in formula (I) adulterates carbon nitride photocatalyst in aqueous, described inorganic ion all solutions from and be combined with the raw molecule preparing carbonitride, obtain under high-temperature roasting inorganic ions doping carbon nitride photocatalyst; Meanwhile, described inorganic ions enters into carbonitride layer structure, obtains the inorganic ions doping carbon nitride photocatalyst with molecular formula shown in formula (I).Inorganic ions doping carbon nitride photocatalyst provided by the invention is at C 3n 4be mixed with inorganic ions in layer structure, make its energy gap be decreased to 2.2eV ~ 2.6eV, its absorption spectrum is from generation red shift, and therefore, inorganic ions doping carbon nitride photocatalyst provided by the invention can absorb more visible ray.Experimental result shows, inorganic ions doping carbon nitride photocatalyst provided by the invention can realize the removal to NO under the irradiation of visible ray, and it is 30% ~ 50% to the clearance of NO, substantially increase under visible light to the removal of NO, this illustrates that inorganic ions provided by the invention doping carbon nitride photocatalyst has higher visible light catalysis activity.
In addition, the form of inorganic ions provided by the invention doping carbon nitride photocatalyst is the two-dimensional structure that the carbon nitride photocatalyst of the inorganic ions doping with molecular formula shown in formula (I) has stratiform, two-dimensional structure and the inorganic ions of stratiform are conducive to being separated of photogenerated charge and transmission, improve catalytic efficiency, improve the utilization rate to light source, therefore, the carbon nitride photocatalyst of inorganic ions doping provided by the invention has higher photocatalysis performance.
In order to further illustrate the present invention, below in conjunction with embodiment, carbon nitride photocatalyst that inorganic ions provided by the invention adulterates and preparation method thereof is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
By deionized water, 0.126g potassium chloride is dissolved, and in Klorvess Liquid, add the mono-cyanogen ammonia of 4g fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 2h under 550 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of potassium chloride doping carbon nitride photocatalyst prepared by the present embodiment is [KCl] 0.03[C 3n 4] 0.97.
The potassium chloride obtained doping carbon nitride photocatalyst is carried out UV-vis DRS analysis by the present invention, and result as shown in Figure 1.Result shows, the energy gap of potassium chloride doping carbon nitride photocatalyst prepared by the present embodiment is 2.52eV, has significantly absorb visible ray; The potassium chloride obtained doping carbon nitride photocatalyst is carried out PL analysis by the present invention, result as shown in Figure 2, result shows, the carbon nitride photocatalyst that the PL strength ratio of potassium chloride doping carbon nitride photocatalyst prepared by the present embodiment is pure obviously reduces, and light induced electron is enhanced with being separated of hole.
The potassium chloride obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g potassium chloride doping carbon nitride photocatalyst embodiment 1 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated potassium chloride doping carbon nitride photocatalyst, the clearance obtaining NO is 31.3%, result is as shown in table 1, the catalytic performance result of the potassium chloride doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, potassium chloride doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 2
By deionized water, 0.089g KBr is dissolved, and in potassium bromide solution, add 4g dicyan diamino fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 3h under 500 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of KBr doping carbon nitride photocatalyst prepared by the present embodiment is [KBr] 0.05[C 3n 4] 0.95.
The KBr obtained doping carbon nitride photocatalyst is carried out sem analysis by the present invention, and result as shown in Figure 3.As seen from Figure 3, the KBr doping carbon nitride photocatalyst that the present embodiment obtains is the nanometer sheet structure of two-dimensional layer, and the doping of KBr does not damage the structure of carbonitride.
The KBr obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g KBr doping carbon nitride photocatalyst embodiment 2 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated KBr doping carbon nitride photocatalyst, the clearance obtaining NO is 38.5%, result is as shown in table 1, the catalytic performance result of the KBr doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, KBr doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 3
By deionized water, 0.078g KI is dissolved, and in liquor kalii iodide, add 4g melamine fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 4h under 520 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of KI doping carbon nitride photocatalyst prepared by the present embodiment is [KI] 0.07[C 3n 4] 0.93.The KI obtained doping carbon nitride photocatalyst is carried out UV-vis DRS analysis by the present invention, and result as shown in Figure 4.Result shows, the energy gap of KI doping carbon nitride photocatalyst prepared by the present embodiment is 2.47eV, has significantly absorb visible ray.
The KI obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g KI doping carbon nitride photocatalyst embodiment 3 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated KI doping carbon nitride photocatalyst, the clearance obtaining NO is 39.7%, result is as shown in table 1, the catalytic performance result of the KI doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, KI doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 4
By deionized water by 0.054g chloride leach, and in ammonium chloride solution, add 4g cyanuric acid fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 3h under 560 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The ammonium chloride obtained doping carbon nitride photocatalyst is carried out XRD analysis by the present invention, result as shown in Figure 5, Fig. 5 is the XRD collection of illustrative plates of ammonium chloride doping carbon nitride photocatalyst prepared by the embodiment of the present invention 4, as seen from Figure 5, the thing of ammonium chloride doping carbon nitride photocatalyst that obtains of the present embodiment is mutually for C 3n 4.Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [NH 4cl] 0.03[C 3n 4] 0.97.
The ammonium chloride obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g ammonium chloride doping carbon nitride photocatalyst embodiment 4 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated ammonium chloride doping carbon nitride photocatalyst, the clearance obtaining NO is 38.4%, result is as shown in table 1, the catalytic performance result of the ammonium chloride doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, ammonium chloride doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 5
By deionized water, 0.074g ammonium bromide is dissolved, and in ammonium bromide solution, add 10g thiocarbamide fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 2h under 580 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [NH 4br] 0.1[C 3n 4] 0.9.
The ammonium bromide obtained doping carbon nitride photocatalyst is carried out XRD analysis by the present invention, result as shown in Figure 6, Fig. 6 is the XRD collection of illustrative plates of ammonium bromide doping carbon nitride photocatalyst prepared by the embodiment of the present invention 5, as seen from Figure 6, the thing of ammonium chloride doping carbon nitride photocatalyst that obtains of the present embodiment is mutually for C 3n 4.
The ammonium bromide obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g ammonium bromide doping carbon nitride photocatalyst embodiment 5 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated ammonium bromide doping carbon nitride photocatalyst, the clearance obtaining NO is 39.1%, result is as shown in table 1, the catalytic performance result of the ammonium bromide doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, ammonium bromide doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 6
By deionized water, 0.069g ammonium iodide is dissolved, and in ammonium iodide solution, add 10g urea fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 3h under 600 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [NH 4i] 0.15[C 3n 4] 0.85.
The ammonium iodide obtained doping carbon nitride photocatalyst is carried out the removal of NO by the present invention, result as shown in Figure 7, as seen from Figure 7, the clearance to NO of the ammonium iodide doping carbon nitride photocatalyst that the present embodiment obtains is 48.7%, has larger enhancing than the removal of unadulterated carbonitride to NO.
The ammonium iodide obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g ammonium iodide doping carbon nitride photocatalyst embodiment 6 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated ammonium iodide doping carbon nitride photocatalyst, the clearance obtaining NO is 48.7%, result is as shown in table 1, the catalytic performance result of the ammonium iodide doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, ammonium iodide doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 7
By deionized water, 0.159g potassium nitrate is dissolved, and in potassium nitrate solution, add 10g thiocarbamide fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 4h under 500 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out the analysis of SEM Surface scan to the photochemical catalyst that the present invention obtains, as seen from Figure 19, containing potassium, oxygen, carbon and nitrogen element in the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment, and catalyst doped chemical is evenly distributed result.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [KNO 3] 0.02[C 3n 4] 0.98.
The potassium nitrate obtained doping carbon nitride photocatalyst is carried out tem analysis by the present invention, result as shown in Figure 8, as seen from Figure 8, the potassium nitrate doping carbon nitride photocatalyst that the present embodiment obtains is that two-dimensional nano is laminar structured, and potassium nitrate doping carbonitride does not damage the body construction of carbonitride.
The potassium nitrate obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g potassium nitrate doping carbon nitride photocatalyst embodiment 7 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated potassium nitrate doping carbon nitride photocatalyst, the clearance obtaining NO is 44.6%, result is as shown in table 1, the catalytic performance result of the potassium nitrate doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, potassium nitrate doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Fig. 9 is the energy spectrogram of the carbon nitride photocatalyst of potassium nitrate doping prepared by the embodiment of the present invention 7.
Embodiment 8
By deionized water, 0.158g potassium sulfate is dissolved, and in potassium sulfate solution, add 10g urea fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 2h under 500 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out the analysis of SEM Surface scan to the photochemical catalyst that the present invention obtains, as seen from Figure 20, containing potassium, oxygen, sulphur, carbon and nitrogen element in the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment, and doped chemical is evenly distributed result.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [K 2sO 4] 0.07[C 3n 4] 0.93.
The potassium sulfate obtained doping carbon nitride photocatalyst is carried out tem analysis by the present invention, result as shown in Figure 10, as seen from Figure 10, the potassium sulfate doping carbon nitride photocatalyst that the present embodiment obtains is that two-dimensional nano is laminar structured, and potassium sulfate doping carbonitride does not damage the body construction of carbonitride.
The potassium sulfate obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g potassium sulfate doping carbon nitride photocatalyst embodiment 8 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated potassium sulfate doping carbon nitride photocatalyst, the clearance obtaining NO is 43.2%, result is as shown in table 1, the catalytic performance result of the potassium sulfate doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, potassium sulfate doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Figure 11 is the energy spectrogram of the carbon nitride photocatalyst of potassium sulfate doping prepared by the embodiment of the present invention 8.
Embodiment 9
By deionized water, 0.213g potash is dissolved, and in solution of potassium carbonate, add the mono-cyanogen ammonia of 4g fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 3h under 480 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [K 2cO 3] 0.05[C 3n 4] 0.95.
The potash obtained doping carbon nitride photocatalyst is carried out XRD analysis by the present invention, result as shown in figure 12, Figure 12 is the XRD collection of illustrative plates of potash doping carbon nitride photocatalyst prepared by the embodiment of the present invention 9, as seen from Figure 12, the thing of potash doping carbon nitride photocatalyst that obtains of the present embodiment is mutually for C 3n 4.
The potash obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g potash doping carbon nitride photocatalyst embodiment 9 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated potash doping carbon nitride photocatalyst, the clearance obtaining NO is 40.5%, result is as shown in table 1, the catalytic performance result of the potash doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, potash doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 10
By deionized water, 0.126g potassium dihydrogen phosphate is dissolved, and in potassium dihydrogen phosphate, add 4g dicyan diamino fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 2h under 520 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [KH 2pO 4] 0.12[C 3n 4] 0.88.
The potassium dihydrogen phosphate obtained doping carbon nitride photocatalyst is carried out UV-vis DRS analysis by the present invention, and as shown in figure 13, Figure 13 is the UV-vis DRS collection of illustrative plates of the carbon nitride photocatalyst of potassium dihydrogen phosphate doping prepared by the embodiment of the present invention 10 to result; Result shows, the energy gap of potassium dihydrogen phosphate doping carbon nitride photocatalyst prepared by the present embodiment is 2.50eV, has significantly absorb visible ray.
The potassium dihydrogen phosphate obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g potash doping carbon nitride photocatalyst embodiment 10 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated potassium dihydrogen phosphate doping carbon nitride photocatalyst, the clearance obtaining NO is 38.7%, result is as shown in table 1, the catalytic performance result of the potassium dihydrogen phosphate doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, potassium dihydrogen phosphate doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 11
By deionized water, 0.124g barium chloride is dissolved, and in barium chloride solution, add 4g melamine fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 2h under 570 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [BaCl 2] 0.13[C 3n 4] 0.87.
The barium chloride obtained doping carbon nitride photocatalyst is carried out sem analysis by the present invention, and as shown in figure 14, Figure 14 is the SEM photo of the carbon nitride photocatalyst of barium chloride doping prepared by the embodiment of the present invention 11 to result; As seen from Figure 14, the barium chloride doping carbon nitride photocatalyst that the present embodiment obtains has stratiform two-dimensional nano chip architecture, and barium chloride doping carbonitride does not damage the structure of carbonitride.
The barium chloride obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g barium chloride doping carbon nitride photocatalyst embodiment 11 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated barium chloride doping carbon nitride photocatalyst, the clearance obtaining NO is 38.3%, result is as shown in table 1, the catalytic performance result of the barium chloride doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, barium chloride doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 12
By deionized water, 0.075g calcium chloride is dissolved, and in calcium chloride solution, add 4g cyanuric acid fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 3h under 500 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [CaCl 2] 0.06[C 3n 4] 0.94.
The calcium chloride obtained doping carbon nitride photocatalyst is carried out UV-vis DRS analysis by the present invention, and as shown in figure 15, result shows result, and the energy gap of calcium chloride doping carbon nitride photocatalyst prepared by the present embodiment is 2.57eV, has significantly absorb visible ray.
The calcium chloride obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g calcium chloride doping carbon nitride photocatalyst embodiment 12 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated calcium chloride doping carbon nitride photocatalyst, the clearance obtaining NO is 37.6%, result is as shown in table 1, the catalytic performance result of the calcium chloride doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, barium chloride doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 13
By deionized water, 0.103g magnesium chloride is dissolved, and in magnesium chloride solution, add 10g thiocarbamide fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 3h under 570 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [MgCl 2] 0.08[C 3n 4] 0.92.
The magnesium chloride obtained doping carbon nitride photocatalyst is carried out the removal of NO by the present invention, result as shown in figure 16, as seen from Figure 16, the clearance to NO of the ammonium iodide doping carbon nitride photocatalyst that the present embodiment obtains is 40.8%, has larger enhancing than the removal of unadulterated carbonitride to NO.
The magnesium chloride obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g magnesium chloride doping carbon nitride photocatalyst embodiment 13 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated magnesium chloride doping carbon nitride photocatalyst, the clearance obtaining NO is 40.8%, result is as shown in table 1, the catalytic performance result of the magnesium chloride doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, magnesium chloride doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 14
By deionized water, 0.081g ammonium sulfate is dissolved, and in ammonium sulfate, add 10g urea fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 4h under 470 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [(NH 4) 2sO 4] 0.15[C 3n 4] 0.85.
The ammonium sulfate obtained doping carbon nitride photocatalyst is carried out the removal of NO by the present invention, result as shown in figure 17, as seen from Figure 17, the clearance to NO of the ammonium sulfate doping carbon nitride photocatalyst that the present embodiment obtains is 44.1%, has larger enhancing than the removal of unadulterated carbonitride to NO.
The ammonium sulfate obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g ammonium sulfate doping carbon nitride photocatalyst embodiment 14 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated ammonium sulfate doping carbon nitride photocatalyst, the clearance obtaining NO is 44.1%, result is as shown in table 1, the catalytic performance result of the ammonium sulfate doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, ammonium sulfate doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 15
By deionized water, 0.061g ammonium nitrate is dissolved, and in ammonium nitrate solution, add the mono-cyanogen ammonia of 4g fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 4h under 600 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [NH 4nO 3] 0.09[C 3n 4] 0.91.
The ammonium nitrate obtained doping carbon nitride photocatalyst is carried out the removal of NO by the present invention, result as shown in figure 18, as seen from Figure 18, the clearance to NO of the ammonium nitrate doping carbon nitride photocatalyst that the present embodiment obtains is 46.9%, has larger enhancing than the removal of unadulterated carbonitride to NO.
The ammonium nitrate obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g ammonium nitrate doping carbon nitride photocatalyst embodiment 15 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated ammonium nitrate doping carbon nitride photocatalyst, the clearance obtaining NO is 46.9%, result is as shown in table 1, the catalytic performance result of the ammonium nitrate doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, ammonium nitrate doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Embodiment 16
By deionized water, 0.074g ammonium carbonate is dissolved, and in sal volatile, add 4g dicyan diamino fully stir and evenly mix.After the mixture of gained is dried under 60 DEG C of conditions, heat treatment 3h under 550 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
Carry out XRD and XPS analysis to the photochemical catalyst obtained, result shows.The molecular formula of the carbon nitride photocatalyst of inorganic ions doping prepared by the present embodiment is [(NH 4) 2cO 3] 0.05[C 3n 4] 0.95.
The ammonium nitrate obtained doping carbon nitride photocatalyst is carried out PL analysis by the present invention, result as shown in figure 19, result shows, the carbon nitride photocatalyst that the PL strength ratio of ammonium nitrate doping carbon nitride photocatalyst prepared by the present embodiment is pure obviously reduces, and light induced electron is enhanced with being separated of hole; The ammonium carbonate obtained doping carbon nitride photocatalyst is carried out the removal of NO by the present invention, result as shown in figure 20, as seen from Figure 20, the clearance to NO of the ammonium carbonate doping carbon nitride photocatalyst that the present embodiment obtains is 38.6%, has larger enhancing than the removal of unadulterated carbonitride to NO.
The ammonium carbonate obtained doping carbon nitride photocatalyst is used for the removal to NO by the present invention, detailed process is as follows: be 60% in relative humidity, oxygen content is under the condition of 21%, 0.2g ammonium carbonate doping carbon nitride photocatalyst embodiment 16 obtained is placed in NO Continuous Flow, the initial concentration of NO is 650ppb, gas flow is 2.4L/min, adopt the halogen tungsten lamp of 100W, and adopt the edge filter filtering ultraviolet light of 420nm, visible light-transmissive is irradiated ammonium carbonate doping carbon nitride photocatalyst, the clearance obtaining NO is 38.6%, result is as shown in table 1, the catalytic performance result of the ammonium carbonate doping carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, ammonium carbonate doping carbon nitride photocatalyst prepared by the present embodiment has higher clearance to NO under the irradiation of visible ray, illustrate that it has higher visible light catalysis activity.
Comparative example 1
After drying under 60 DEG C of conditions after mono-for 4g cyanogen ammonia being dissolved by deionized water, heat treatment 2h under 550 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The carbon nitride photocatalyst prepared by the comparative example obtained carries out PL analysis, result as shown in Figure 2, result shows, the carbon nitride photocatalyst that the PL strength ratio of potassium chloride doping carbon nitride photocatalyst prepared by the present embodiment is pure obviously reduces, and light induced electron is enhanced with being separated of hole.
The potassium chloride doping carbon nitride photocatalyst provided according to embodiment 1 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 20.5% to the clearance of NO.
Comparative example 2
After drying under 60 DEG C of conditions after 4g dicyan diamino being dissolved by deionized water, heat treatment 3h under 500 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The KBr doping carbon nitride photocatalyst provided according to embodiment 2 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 25.3% to the clearance of NO.
Comparative example 3
With deionized water by after 4g melamine goes under 60 DEG C of conditions dry after, heat treatment 4h under 520 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The KI doping carbon nitride photocatalyst provided according to embodiment 3 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 27.8% to the clearance of NO.
Comparative example 4
After drying under 60 DEG C of conditions after 4g cyanuric acid being dissolved by deionized water, heat treatment 3h under 560 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The ammonium chloride doping carbon nitride photocatalyst provided according to embodiment 4 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 26.1% to the clearance of NO.
Comparative example 5
After drying under 60 DEG C of conditions after 10g thiocarbamide being dissolved by deionized water, heat treatment 2h under 580 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The ammonium bromide doping carbon nitride photocatalyst provided according to embodiment 5 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 26.8% to the clearance of NO.
Comparative example 6
After drying under 60 DEG C of conditions after 10g urea being dissolved by deionized water, heat treatment 3h under 600 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The ammonium iodide doping carbon nitride photocatalyst provided according to embodiment 6 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 36.2% to the clearance of NO.
Comparative example 7
After drying under 60 DEG C of conditions after 10g thiocarbamide being dissolved by deionized water, heat treatment 4h under 600 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The potassium nitrate doping carbon nitride photocatalyst provided according to embodiment 7 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 33.5% to the clearance of NO.
Comparative example 8
After drying under 60 DEG C of conditions after 10g urea being dissolved by deionized water, heat treatment 2h under 600 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The potassium sulfate doping carbon nitride photocatalyst provided according to embodiment 8 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 31.7% to the clearance of NO.
Comparative example 9
After drying under 60 DEG C of conditions after mono-for 4g cyanogen ammonia being dissolved by deionized water, heat treatment 3h under 480 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The potash doping carbon nitride photocatalyst provided according to embodiment 9 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 28.6% to the clearance of NO.
Comparative example 10
After drying under 60 DEG C of conditions after 4g dicyan diamino being dissolved by deionized water, heat treatment 2h under 520 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The potassium dihydrogen phosphate doping carbon nitride photocatalyst provided according to embodiment 10 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 26.5% to the clearance of NO.
Comparative example 11
With deionized water by after 4g melamine goes under 60 DEG C of conditions dry after, heat treatment 3h under 570 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The barium chloride doping carbon nitride photocatalyst provided according to embodiment 11 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 27.2% to the clearance of NO.
Comparative example 12
After drying under 60 DEG C of conditions after 4g cyanuric acid being dissolved by deionized water, heat treatment 2h under 500 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The calcium chloride doping carbon nitride photocatalyst provided according to embodiment 12 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 25.4% to the clearance of NO.
Comparative example 13
After drying under 60 DEG C of conditions after 10g thiocarbamide being dissolved by deionized water, heat treatment 3h under 570 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The magnesium chloride doping carbon nitride photocatalyst provided according to embodiment 13 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 29.6% to the clearance of NO.
Comparative example 14
After drying under 60 DEG C of conditions after 10g urea being dissolved by deionized water, heat treatment 4h under 480 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The ammonium sulfate doping carbon nitride photocatalyst provided according to embodiment 14 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 32.9% to the clearance of NO.
Comparative example 15
After drying under 60 DEG C of conditions after mono-for 4g cyanogen ammonia being dissolved by deionized water, heat treatment 4h under 600 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The ammonium nitrate doping carbon nitride photocatalyst provided according to embodiment 15 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 34.7% to the clearance of NO.
Comparative example 16
After drying under 60 DEG C of conditions after 4g dicyan diamino being dissolved by deionized water, heat treatment 3h under 550 DEG C of conditions.Be cooled to after room temperature until temperature, product be milled into powder with for subsequent use.
The carbon nitride photocatalyst prepared by the comparative example obtained carries out PL analysis, result as shown in figure 17, result shows, the carbon nitride photocatalyst that the PL strength ratio of potassium chloride doping carbon nitride photocatalyst prepared by the present embodiment is pure obviously reduces, and light induced electron is enhanced with being separated of hole.
The ammonium carbonate doping carbon nitride photocatalyst provided according to embodiment 16 is to the minimizing technology of NO, the catalytic performance of the carbon nitride photocatalyst that this comparative example obtains is detected, result is as shown in table 1, the catalytic performance result of the carbon nitride photocatalyst that table 1 obtains for the embodiment of the present invention and comparative example, as can be seen from Table 1, the catalytic activity of carbon nitride photocatalyst to visible ray prepared by this comparative example is poor, under the irradiation of visible ray, is only 27.7% to the clearance of NO.
The catalytic performance result of the carbonitride series photocatalyst that table 1 embodiment of the present invention and comparative example obtain
Numbering NO clearance (%)
Embodiment 1 31.3
Comparative example 1 20.5
Embodiment 2 38.5
Comparative example 2 25.3
Embodiment 3 39.7
Comparative example 3 27.8
Embodiment 4 38.4
Comparative example 4 26.1
Embodiment 5 39.1
Comparative example 5 26.8
Embodiment 6 48.7
Comparative example 6 36.2
Embodiment 7 44.6
Comparative example 7 33.5
Embodiment 8 43.2
Comparative example 8 31.7
Embodiment 9 40.5
Comparative example 9 28.6
Embodiment 10 38.7
Comparative example 10 26.5
Embodiment 11 38.3
Comparative example 11 27.2
Embodiment 12 37.6
Comparative example 12 25.4
Embodiment 13 40.8
Comparative example 13 29.6
Embodiment 14 44.1
Comparative example 14 32.9
Embodiment 15 46.9
Comparative example 15 34.7
Embodiment 16 38.6
Comparative example 16 27.7
As can be seen from Table 1, inorganic ions doping carbon nitride photocatalyst provided by the invention has higher visible light catalysis activity.
As seen from the above embodiment, inorganic ions doping carbon nitride photocatalyst provided by the invention has the molecular formula shown in formula (I): [X] m[C 3n 4] (1-m)(I); Wherein, m is 1% ~ 50%.The present invention using single cyanogen ammonia, dicyan diamino, melamine, cyanuric acid, thiocarbamide or urea as the raw material preparing carbonitride, using potassium chloride, KBr, KI, ammonium chloride, ammonium bromide, ammonium iodide, potassium nitrate, potassium sulfate, potash, potassium dihydrogen phosphate, calcium chloride, magnesium chloride, barium chloride, ammonium sulfate, ammonium nitrate or ammonium carbonate as inorganic salt raw material.Dry under 60 DEG C of conditions after the raw material and inorganic salt raw material of preparing carbonitride are fully mixed in aqueous, then heat treatment under the high temperature conditions, obtain the inorganic ions doping carbon nitride photocatalyst with molecular formula shown in formula (I).C provided by the invention 3n 4in photochemical catalyst, inorganic ions enters into C 3n 4lattice in or in interbed, the doping of inorganic ions exists and makes C provided by the invention 3n 4photochemical catalyst has higher visible light catalysis activity.Experiment shows, the inorganic ions doping C with two-dimensional structure provided by the invention 3n 4the visible light catalysis activity of photochemical catalyst is the C that do not adulterate 3n 41.5 ~ 3 times of photochemical catalyst.In addition, preparation method's mild condition provided by the invention, simple to operate, be beneficial to its large-scale production.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (9)

1. a carbon nitride photocatalyst for inorganic ions doping, has the molecular formula shown in formula (I):
[X] m[C 3N 4] (1-m)(I)；
Wherein, m is 1% ~ 40%;
X is KCl, KBr, KI, K 2sO 4, K 2cO 3, KH 2pO 4, CaCl 2, MgCl 2, BaCl 2.
2. the carbon nitride photocatalyst of inorganic ions doping according to claim 1, it is characterized in that, described m is 2% ~ 20%.
3. a preparation method for the carbon nitride photocatalyst of inorganic ions doping, comprises the following steps:
Carbon nitrogen source and inorganic salts are fully mixed post-drying in aqueous, calcine, obtain the carbon nitride photocatalyst of the inorganic ions doping with molecular formula shown in formula (I):
[X] m[C 3N 4] (1-m)(I)；
Wherein, m is 1% ~ 20%;
Described inorganic salts are KCl, KBr, KI, K 2sO 4, K 2cO 3, KH 2pO 4, CaCl 2, MgCl 2, BaCl 2.
4. preparation method according to claim 3, is characterized in that, described carbon nitrogen source is single cyanogen ammonia, dicyanodiamine, melamine, cyanuric acid, thiocarbamide or urea.
5. preparation method according to claim 3, is characterized in that, the mass ratio of described carbon nitrogen source and described inorganic salts is 1:(0.01 ~ 0.4).
6. preparation method according to claim 5, is characterized in that, the mass ratio of described carbon nitrogen source and described inorganic salts is 1:(0.02 ~ 0.2).
7. preparation method according to claim 3, is characterized in that, described bake out temperature is 40 ~ 70 DEG C.
8. preparation method according to claim 7, is characterized in that, described calcining heat is 400 ~ 650 DEG C.
9. preparation method according to claim 3, is characterized in that, described calcination time is 0.5 ~ 10h.
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