CN103736513B - A kind of TiO 2(B) g-C 3n 4the preparation method of composite nano plate photochemical catalyst - Google Patents
A kind of TiO 2(B) g-C 3n 4the preparation method of composite nano plate photochemical catalyst Download PDFInfo
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000002055 nanoplate Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 51
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
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- 239000003344 environmental pollutant Substances 0.000 abstract 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 14
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- 238000002835 absorbance Methods 0.000 description 7
- 239000005030 aluminium foil Substances 0.000 description 7
- 239000007857 degradation product Substances 0.000 description 7
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- 229910052724 xenon Inorganic materials 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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Abstract
A kind of TiO
2(B) g-C
3n
4the preparation method of composite nano plate photochemical catalyst, belongs to catalysis material technical field.The method comprises the steps: (1) by g-C
3n
4with TiO
2colloidal sol mixes, and carries out water bath with thermostatic control stirring at 60 ~ 90 DEG C; (2) above-mentioned slurry is carried out solvent heat treatment at 140 ~ 180 DEG C, obtain described TiO
2(B) g-C
3n
4composite nano plate photochemical catalyst.TiO provided by the invention
2(B) g-C
3n
4nanometer sheet has good photocatalytic pollutant degradation and photocurrent response performance; Preparation method provided by the invention, have that raw material is inexpensive, technique is simple, structure-controllable etc., prepared photochemical catalyst has very high application prospect and practical value in sewage disposal, atmospheric treatment.
Description
Technical field
The present invention relates to a kind of TiO
2(B) g-C
3n
4the preparation method of composite nano plate photochemical catalyst, belongs to catalysis material technical field.
Background technology
Nano-TiO
2photochemical catalyst is the class attracted most attention in catalysis material family, there is efficient, stable chemical nature, the advantage such as nontoxic, cheap, it is the main study subject in photocatalysis and opto-electronic conversion field between self-discovery so far more than 40 year always, also be the catalysis material being hopeful large-scale practical application most, can be used for deodorizing under sunshine or indoor light, antibacterial, decolouring and automatically cleaning etc.But nano-TiO
2still be apparent not enough in the utilizing of photocatalysis efficiency and visible ray, especially the latter constrains TiO to a certain extent
2the practical engineering application of photocatalysis technology.TiO
2energy gap (E
g) be 3.2eV, corresponding light absorption band edge is 387nm, can only excite by the ultraviolet radiation less than 5% in solar spectrum, and the visible light part in solar energy can not be made full use of; On the other hand, TiO
2photoinduced electron-hole-recombination probability very high, only have an appointment 1% exciton finally move to surface participate in reaction, cause photo-generated carrier utilization ratio low.Therefore, to TiO
2carrying out modification, expand the utilization ratio in its effective photoresponse scope and raising light induced electron and hole, improve light-catalyzed reaction activity, is the basis of photocatalysis treatment environmental pollution application.
By semiconductor coupling, the separation in photoinduced electron-hole can be promoted, reduce recombination probability, improve the quantum efficiency of catalysis material, when the absorption band edge of couple semiconductor is in visible-range, can TiO be widened
2absorb the wave-length coverage of exciting light, thus obtain the high-efficiency photocatalysis material utilizing ambient light catalytic oxidation.Nitrogen carbide (C
3n
4) be the novel organic polymer semiconductor material of a class, to be characterized in: 1. constitution element is only C and N, and not containing metal element that abundant raw material and very cheap does not exist the problem of resource exhaustion, has the layer structure and conjugated electrons structure that are similar to graphite; 2. there is suitable band gap, E
g~ 2.7eV, can absorb the visible ray being no more than 460nm, C
3n
4band edge position and TiO
2good II type semiconductor coupling can be formed, be conducive to the separation of quantity of photogenerated charge; 3. preparation method is simple, can obtain C by the presoma thermal polymerization of being rich in C, N
3n
4, inter-layer bonding force is weak, is easy to peel off, and to heat, acid, alkali all has good stability.These advantages make C
3n
4in the application great potential of photocatalysis and photodissociation hydrogen preparation field.By C
3n
4and TiO
2carry out hydridization coupling, under nanoscale, carry out structure regulating and constituent optimization, play that respective performance advantage is collaborative to be strengthened, can be used for the purification of indoor and outdoor water and air, reach taste removal, antibacterial object and without the need to artificial servo.Prior art adopts high-temperature calcination to prepare g-C usually
3n
4composite photo-catalyst, shortcoming is that component and structure are difficult to accurate control, and distribution of each phase is uneven.
Summary of the invention
The object of this invention is to provide a kind of environmental protection, simple and easy controlled TiO
2(B) g-C
3n
4photochemical catalyst preparation method, method of the present invention adopts crystal seed induced growth, can accurate control TiO
2(B) nanometer sheet and g-C
3n
4the distribution of nanometer sheet two-phase, effectively controls component relative amount and special construction simultaneously; TiO prepared by method of the present invention
2(B) g-C
3n
4nanosheet photocatalyst has good photoelectric properties.
TiO of the present invention
2(B) g-C
3n
4composite nano plate photochemical catalyst is TiO
2(B) nanometer sheet growth is at g-C
3n
4in nanometer sheet.
A kind of TiO
2(B) g-C
3n
4the preparation method of composite nano plate photochemical catalyst, comprises the steps:
(1) by g-C
3n
4with TiO
2colloidal sol mixes and adds ammoniacal liquor, carries out water bath with thermostatic control stirring at 60 ~ 90 DEG C;
(2) step (1) slurry is carried out solvent heat treatment at 140 ~ 180 DEG C, obtain described TiO
2(B) g-C
3n
4composite nano plate photochemical catalyst.
In step (1), described g-C
3n
4by urea, 550 DEG C of calcinings are obtained in atmosphere, and calcining heating rate is 10 DEG C/min ~ 20 DEG C/min.
In step (1), described water bath processing temperature is 60 ~ 90 DEG C, and constant temperature time is 0.5 ~ 2 hour.
In step (2), described TiO
2colloidal sol is TiCl
3or TiCl
4in a kind of colloidal sol being dissolved in ethylene glycol gained, preferably adopt TiCl
4.
In step (2), the ratio of described raw material is g-C
3n
4: TiCl
3or TiCl
4: ethylene glycol: ammoniacal liquor=0.1g:(0.1 ~ 0.5mL) or (0.2 ~ 1mL): (30 ~ 60mL): (1 ~ 4mL).
In step (2), described solvent heat treatment temperature is 140 ~ 180 DEG C, and constant temperature time is 6 ~ 48 hours.
TiO provided by the invention
2(B) g-C
3n
4composite nano plate photochemical catalyst has good photocatalysis degradation organic contaminant and photocurrent response performance; Preparation method provided by the invention, its raw material is inexpensive, technique simple, has very high application prospect and practical value.
Accompanying drawing explanation
Fig. 1 is the XRD comparison diagram of each CNTO sample of different condition in embodiment;
Fig. 2 prepares g-C in embodiment
3n
4tEM figure;
Fig. 3 is the TEM figure of the CNTO-1 of preparation in embodiment 1;
Fig. 4 is the TEM figure of the CNTO-3 of preparation in embodiment 3;
Fig. 5 be in embodiment each CNTO sample under visible light to MB degradation property comparison diagram;
Fig. 6 prepares g-C in embodiment
3n
4with the PL spectrogram of the CNTO-3 of preparation in embodiment 3;
Fig. 7 prepares g-C in embodiment
3n
4with the photoelectric current performance test spectrogram of the CNTO-3 of preparation in embodiment 3.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Experimental example 1:
Get urea 10g and be placed in crucible, with aluminium-foil paper by tight for crucible parcel, be placed in Muffle furnace 550 DEG C of calcinings in air atmosphere, heating rate is 10 DEG C/min, and naturally cool after insulation 4h, gained powder is g-C
3n
4.Get g-C
3n
4powder 0.1g, with 0.2mlTiCl
4, 30ml ethylene glycol, 1mL concentrated ammonia liquor make slurry, 60 DEG C of stirring in water bath 2h, has been incubated rear immigration autoclave, airtightly puts into air dry oven 140 DEG C insulation 48h.After reaction, powder is leached, namely obtain TiO with after deionized water, alcohol flushing, drying respectively
2(B) g-C
3n
4composite nano plate photochemical catalyst, is designated as CNTO-1.With methylene blue (MB) as target degradation product, get TiO
2(B) g-C
3n
4it is in the MB solution of 10mg/L that composite nano plate photochemical catalyst (CNTO-1) 50mg joins 50ml concentration, after ultrasonic 3min, 2h is stirred in dark place, makes it to reach adsorption-desorption balance, after adsorption equilibrium process, reaction vessel is placed in irradiation under 300W xenon source, add 420nm optical filter, according to time-division sampling, and get MB supernatant liquor and survey its absorbance A, MB concentration in solution is calculated according to Lambert-Beer's law, then according to formula ln(C/C
0) calculate its degradation rate.Wherein C temporally samples MB concentration, C
0for the concentration of original MB solution when adsorption-desorption balances.
Experimental example 2:
Get urea 10g and be placed in crucible, with aluminium-foil paper by tight for crucible parcel, be placed in Muffle furnace 550 DEG C of calcinings in air atmosphere, heating rate is 15 DEG C/min, and naturally cool after insulation 4h, gained powder is g-C
3n
4.Get g-C
3n
4powder 0.1g, with 0.5mlTiCl
4, 40ml ethylene glycol, 2mL concentrated ammonia liquor make slurry, 60 DEG C of stirring in water bath 1h, has been incubated rear immigration autoclave, airtightly puts into air dry oven 140 DEG C insulation 36h.After reaction, powder is leached, namely obtain TiO with after deionized water, alcohol flushing, drying respectively
2(B) g-C
3n
4composite nano plate photochemical catalyst, is designated as CNTO-2.With methylene blue (MB) as target degradation product, get TiO
2(B) g-C
3n
4it is in the MB solution of 10mg/L that composite nano plate photochemical catalyst (CNTO-2) 50mg joins 50ml concentration, after ultrasonic 3min, 2h is stirred in dark place, makes it to reach adsorption-desorption balance, after adsorption equilibrium process, reaction vessel is placed in irradiation under 300W xenon source, add 420nm optical filter, according to time-division sampling, and get MB supernatant liquor and survey its absorbance A, MB concentration in solution is calculated according to Lambert-Beer's law, then according to formula ln(C/C
0) calculate its degradation rate.Wherein C temporally samples MB concentration, C
0for the concentration of original MB solution when adsorption-desorption balances.
Experimental example 3:
Get urea 10g and be placed in crucible, with aluminium-foil paper by tight for crucible parcel, be placed in Muffle furnace 550 DEG C of calcinings in air atmosphere, heating rate is 20 DEG C/min, and naturally cool after insulation 4h, gained powder is g-C
3n
4.Get g-C
3n
4powder 0.1g, with 1mlTiCl
4, 35ml ethylene glycol, 2mL concentrated ammonia liquor make slurry, 70 DEG C of stirring in water bath 1h, has been incubated rear immigration autoclave, airtightly puts into air dry oven 150 DEG C insulation 24h.After reaction, powder is leached, namely obtain TiO with after deionized water, alcohol flushing, drying respectively
2(B) g-C
3n
4composite nano plate photochemical catalyst, is designated as CNTO-3.With methylene blue (MB) as target degradation product, get TiO
2(B) g-C
3n
4it is in the MB solution of 10mg/L that composite nano plate photochemical catalyst (CNTO-3) 50mg joins 50ml concentration, after ultrasonic 3min, 2h is stirred in dark place, makes it to reach adsorption-desorption balance, after adsorption equilibrium process, reaction vessel is placed in irradiation under 300W xenon source, add 420nm optical filter, according to time-division sampling, and get MB supernatant liquor and survey its absorbance A, MB concentration in solution is calculated according to Lambert-Beer's law, then according to formula ln(C/C
0) calculate its degradation rate.Wherein C temporally samples MB concentration, C
0for the concentration of original MB solution when adsorption-desorption balances.
Experimental example 4:
Get urea 10g and be placed in crucible, with aluminium-foil paper by tight for crucible parcel, be placed in Muffle furnace 550 DEG C of calcinings in air atmosphere, heating rate is 18 DEG C/min, and naturally cool after insulation 4h, gained powder is g-C
3n
4.Get g-C
3n
4powder 0.1g, with 0.5mlTiCl
4, 50ml ethylene glycol, 3mL concentrated ammonia liquor make slurry, 80 DEG C of stirring in water bath 1h, has been incubated rear immigration autoclave, airtightly puts into air dry oven 180 DEG C insulation 12h.After reaction, powder is leached, namely obtain TiO with after deionized water, alcohol flushing, drying respectively
2(B) g-C
3n
4composite nano plate photochemical catalyst, is designated as CNTO-4.With methylene blue (MB) as target degradation product, get TiO
2(B) g-C
3n
4it is in the MB solution of 10mg/L that composite nano plate photochemical catalyst (CNTO-4) 50mg joins 50ml concentration, after ultrasonic 3min, 2h is stirred in dark place, makes it to reach adsorption-desorption balance, after adsorption equilibrium process, reaction vessel is placed in irradiation under 300W xenon source, add 420nm optical filter, according to time-division sampling, and get MB supernatant liquor and survey its absorbance A, MB concentration in solution is calculated according to Lambert-Beer's law, then according to formula ln(C/C
0) calculate its degradation rate.Wherein C temporally samples MB concentration, C
0for the concentration of original MB solution when adsorption-desorption balances.
Experimental example 5:
Get urea 10g and be placed in crucible, with aluminium-foil paper by tight for crucible parcel, be placed in Muffle furnace 550 DEG C of calcinings in air atmosphere, heating rate is 20 DEG C/min, and naturally cool after insulation 4h, gained powder is g-C
3n
4.Get g-C
3n
4powder 0.1g, with 1mlTiCl
4, 60ml ethylene glycol, 4mL concentrated ammonia liquor make slurry, 90 DEG C of stirring in water bath 0.5h, has been incubated rear immigration autoclave, airtightly puts into air dry oven 180 DEG C insulation 6h.After reaction, powder is leached, namely obtain TiO with after deionized water, alcohol flushing, drying respectively
2(B) g-C
3n
4composite nano plate photochemical catalyst, is designated as CNTO-5.With methylene blue (MB) as target degradation product, get TiO
2(B) g-C
3n
4it is in the MB solution of 10mg/L that composite nano plate photochemical catalyst (CNTO-5) 50mg joins 50ml concentration, after ultrasonic 3min, 2h is stirred in dark place, makes it to reach adsorption-desorption balance, after adsorption equilibrium process, reaction vessel is placed in irradiation under 300W xenon source, add 420nm optical filter, according to time-division sampling, and get MB supernatant liquor and survey its absorbance A, MB concentration in solution is calculated according to Lambert-Beer's law, then according to formula ln(C/C
0) calculate its degradation rate.Wherein C temporally samples MB concentration, C
0for the concentration of original MB solution when adsorption-desorption balances.
Experimental example 6:
Get urea 10g and be placed in crucible, with aluminium-foil paper by tight for crucible parcel, be placed in Muffle furnace 550 DEG C of calcinings in air atmosphere, heating rate is 20 DEG C/min, and naturally cool after insulation 4h, gained powder is g-C
3n
4.Get g-C
3n
4powder 0.1g, with 0.1mlTiCl
3, 35ml ethylene glycol, 2mL concentrated ammonia liquor make slurry, 70 DEG C of stirring in water bath 1h, has been incubated rear immigration autoclave, airtightly puts into air dry oven 150 DEG C insulation 24h.After reaction, powder is leached, namely obtain TiO with after deionized water, alcohol flushing, drying respectively
2(B) g-C
3n
4composite nano plate photochemical catalyst, is designated as CNTO-6.With methylene blue (MB) as target degradation product, get TiO
2(B) g-C
3n
4it is in the MB solution of 10mg/L that composite nano plate photochemical catalyst (CNTO-6) 50mg joins 50ml concentration, after ultrasonic 3min, 2h is stirred in dark place, makes it to reach adsorption-desorption balance, after adsorption equilibrium process, reaction vessel is placed in irradiation under 300W xenon source, add 420nm optical filter, according to time-division sampling, and get MB supernatant liquor and survey its absorbance A, MB concentration in solution is calculated according to Lambert-Beer's law, then according to formula ln(C/C
0) calculate its degradation rate.Wherein C temporally samples MB concentration, C
0for the concentration of original MB solution when adsorption-desorption balances.
Experimental example 7:
Get urea 10g and be placed in crucible, with aluminium-foil paper by tight for crucible parcel, be placed in Muffle furnace 550 DEG C of calcinings in air atmosphere, heating rate is 20 DEG C/min, and naturally cool after insulation 4h, gained powder is g-C
3n
4.Get g-C
3n
4powder 0.1g, with 0.5mlTiCl
3, 35ml ethylene glycol, 2mL concentrated ammonia liquor make slurry, 70 DEG C of stirring in water bath 1h, has been incubated rear immigration autoclave, airtightly puts into air dry oven 150 DEG C insulation 24h.After reaction, powder is leached, namely obtain TiO with after deionized water, alcohol flushing, drying respectively
2(B) g-C
3n
4composite nano plate photochemical catalyst, is designated as CNTO-7.With methylene blue (MB) as target degradation product, get TiO
2(B) g-C
3n
4it is in the MB solution of 10mg/L that composite nano plate photochemical catalyst (CNTO-7) 50mg joins 50ml concentration, after ultrasonic 3min, 2h is stirred in dark place, makes it to reach adsorption-desorption balance, after adsorption equilibrium process, reaction vessel is placed in irradiation under 300W xenon source, add 420nm optical filter, according to time-division sampling, and get MB supernatant liquor and survey its absorbance A, MB concentration in solution is calculated according to Lambert-Beer's law, then according to formula ln(C/C
0) calculate its degradation rate.Wherein C temporally samples MB concentration, C
0for the concentration of original MB solution when adsorption-desorption balances.
| Sample name | Specific area (m 2/g） | Pore volume (cm 3/g） |
| CN550u | 48.97 | 0.315 |
| CNTO-1 | 277.35 | 0.266 |
| CNTO-2 | 288.56 | 0.309 |
| CNTO-3 | 311.91 | 0.342 |
| CNTO-4 | 290.76 | 0.311 |
| CNTO-5 | 330.85 | 0.356 |
| TiO 2 | 342.34 | 0.263 |
Table 1 is specific area and the pore volume contrast of each CNTO sample of different condition in embodiment.
Claims (7)
1. a TiO
2(B) g-C
3n
4the preparation method of composite nano plate photochemical catalyst, is characterized in that, comprises the steps:
(1) by g-C
3n
4with TiO
2colloidal sol mixes and adds ammoniacal liquor, carries out water bath with thermostatic control stirring at 60 ~ 90 DEG C; Described TiO
2colloidal sol is TiCl
3or TiCl
4in a kind of colloidal sol being dissolved in ethylene glycol gained;
(2) step (1) slurry is carried out solvent heat treatment at 140 ~ 180 DEG C, obtain described TiO
2(B) g-C
3n
4composite nano plate photochemical catalyst;
Raw materials used ratio is g-C
3n
4: TiCl
3: ethylene glycol: ammoniacal liquor=0.1g:(0.1 ~ 0.5mL): (30 ~ 60mL): (1 ~ 4mL); g-C
3n
4: TiCl
4: ethylene glycol: ammoniacal liquor=0.1g:(0.2 ~ 1mL): (30 ~ 60mL): (1 ~ 4mL).
2., according to the method for claim 1, it is characterized in that, in step (1), described g-C
3n
4by urea, 550 DEG C of calcinings are obtained in atmosphere, and calcining heating rate is 10 DEG C/min ~ 20 DEG C/min.
3. according to the method for claim 1, it is characterized in that, in step (1), water bath processing temperature is 60 ~ 90 DEG C, and constant temperature time is 0.5 ~ 2 hour.
4., according to the method for claim 1, it is characterized in that, in step (1), described TiO
2colloidal sol is TiCl
4be dissolved in the colloidal sol of ethylene glycol gained.
5. according to the method for claim 1, it is characterized in that, in step (2), described solvent heat treatment temperature is 140 ~ 180 DEG C, and constant temperature time is 6 ~ 48 hours.
6. according to the TiO that the either method of claim 1-5 obtains
2(B) g-C
3n
4composite nano plate photochemical catalyst.
7. according to the TiO that the either method of claim 1-5 obtains
2(B) g-C
3n
4composite nano plate photochemical catalyst is used for photocatalytic degradation methylene blue.
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|---|---|---|---|
| CN201410003970.7A CN103736513B (en) | 2014-01-03 | 2014-01-03 | A kind of TiO 2(B) g-C 3n 4the preparation method of composite nano plate photochemical catalyst |
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|---|---|---|---|
| CN201410003970.7A CN103736513B (en) | 2014-01-03 | 2014-01-03 | A kind of TiO 2(B) g-C 3n 4the preparation method of composite nano plate photochemical catalyst |
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| Publication Number | Publication Date |
|---|---|
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| CN103736513B true CN103736513B (en) | 2016-03-02 |
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| DE102015014883A1 (en) * | 2015-11-14 | 2017-05-18 | Alzchem Ag | Use of carbonitrides for the photocatalytic reduction of nitrogen oxides |
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| CN106185847A (en) * | 2016-07-01 | 2016-12-07 | 陕西科技大学 | A kind of low-density ultralight carbonitride raw powder's production technology with oriented growth |
| CN107952423A (en) * | 2016-10-18 | 2018-04-24 | 天津大学 | A kind of titanium dioxide high-efficiency photocatalysis material of 2D and preparation method thereof |
| CN107081166B (en) * | 2017-06-12 | 2019-11-05 | 青岛科技大学 | A kind of multilevel structure g-C3N4/TiO2Preparation method |
| CN107362817A (en) * | 2017-06-26 | 2017-11-21 | 上海电力学院 | A kind of preparation method of the adjustable titania modified graphite phase carbon nitride photochemical catalyst of dimension |
| CN107199046B (en) * | 2017-07-19 | 2019-07-12 | 南昌航空大学 | A kind of preparation method of three four/titanium dioxide composite photocatalyst of nitrogen of g- carbon of sandwiched configuration |
| CN108465477A (en) * | 2018-04-03 | 2018-08-31 | 南京大学 | The Preparation method and use of Three-element composite photocatalyst |
| CN108654675B (en) * | 2018-06-05 | 2021-05-18 | 青岛科技大学 | g-C3N4/TiO2(B) Preparation method of composite microspheres |
| CN109174161B (en) * | 2018-10-16 | 2021-05-28 | 西北民族大学 | Magnetically separable TNTs/g-C3N4Preparation method and application of nano composite material |
| CN111250139B (en) * | 2020-02-29 | 2021-07-20 | 青岛科技大学 | Mixed crystal TiO2/g-C3N4Nano hollow tube composite material and preparation method thereof |
| CN114433048A (en) * | 2022-01-20 | 2022-05-06 | 内蒙古农业大学 | In-situ stripping preparation C3N4/TiO2(B) Method and application of micron flower composite catalyst |
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