CN104549500B - A kind of nonmetal liquid phase doping prepares B doping g-C3n4the method of photocatalyst - Google Patents
A kind of nonmetal liquid phase doping prepares B doping g-C3n4the method of photocatalyst Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
A kind of nonmetal liquid phase doping prepares B doping g C3N4The method of photocatalyst, belongs to catalysis material and produces hydrogen technical field.Organic polymer semiconductor material g C prepared by the present invention3N4Photocatalyst is to have selected cheap industrial chemicals carbamide as reactant source, use sodium tetraphenylborate as dopant source, it is surface charge modifying dose with polymine (Polyethyleneimine, PEI), utilizes pyrolysis polymerization simple to operation successfully to prepare.The g C of a kind of nonmetal liquid phase doping modifying and decorating that the present invention provides3N4Photocatalyst has the organizational structure pattern of novelty, good visible light-responded (> 420nm) and photocatalysis hydrogen production performance, promote to be realized with a low cost photocatalysis solar energy conversion new forms of energy；The preparation method that the present invention provides, has the advantages such as inexpensive, the simple process of raw material, has important researching value and industrial applications prospect widely.
Description
Technical field
The present invention relates to photocatalysis field, a kind of nonmetal liquid phase doping prepares B doping g-C3N4The method of photocatalyst, belongs to catalysis material and produces hydrogen technical field.
Background technology
Hydrogen Energy by becoming a kind of very important energy, is paid attention to by various countries on 21 century energy stage.Utilizing Hydrogen Energy is to solve energy problem of China and the effective way of challenge, is also the important guarantee realizing China's sustainable development simultaneously, has the prospect of light in China.But, hydrogen is secondary energy sources, and the method preparing hydrogen at present is the most, and is environment friendliness effective ways by solar photolysis water hydrogen.
In today that energy shortage and environmental pollution are the most serious, exploitation Hydrogen Energy has very major and immediate significance.Each state has the most invested considerable capital to solve future source of energy supply structure problem in scientific research, finds novel regenerative resource.Self-discovery TiO2Optical Electro-Chemistry energy decomposition water produces H2And O2Since, scientific researcher is being made unremitting efforts to for realizing solar photolysis water hydrogen always.But up to the present, the photocatalyst that people are developed generally exists that photoelectric transformation efficiency is low, mostly is only capable of absorbing ultraviolet, and ultraviolet only accounts for about 3% in sunlight, and maximum sunlight intensity is at 500nm.The most how to formulate the current theme that the solution water catalyst of efficient absorption and conversion visible ray then becomes in this research field, how realizing cheap extensive hydrogen manufacturing then becomes research emphasis from now on and final goal.
Polymer semiconductor g-C3N4As a kind of novel nonmetal visible-light photocatalyst, because its unique having of tool is similar to the layer structure of graphite and conjugated electrons structure, high catalytic activity, chemistry with Heat stability is good, nontoxic and preparation is simple, without features such as metals, paid close attention to by whole world research worker, be there is boundless application prospect.But monomer g-C3N4Electron-hole pair recombination rate is higher, causes its activity to be restricted, therefore becomes the focus of research by the modification of photocatalyst is improved photocatalytic activity.
Summary of the invention
Present invention aims to nonmetalloid liquid phase B doping controllable g-C3N4Appearance structure, improve mesoporous quantity, reduce the feature such as recombination rate of photo-generate electron-hole pair, provide a kind of nonmetal liquid phase B doping and modification g-C by simple pyrolysis polyreaction3N4The preparation method of photocatalyst.The method production cost is low, and operating procedure is simple, and the catalyst of preparation has good photocatalysis performance.
The B doping g-C that nonmetal liquid phase doping provided by the present invention is modified3N4Photocatalyst is to be calcined, by carbamide, the g-C obtained3N4In aqueous after positive electricity in surface charge modifying dose of PEI load, more fully adsorb with tetraphenyl boron anion, finally use pyrolysis polymerization synthesis.
The nonmetal liquid phase doping of one provided by the present invention prepares B doping g-C3N4The method of photocatalyst, it is characterised in that comprise the following steps:
(1) by a certain amount of g-C3N4After being placed in distilled water ultrasonic 0.5～2h, continue stirring 12～24h so that it is be sufficiently mixed, obtain g-C3N4Suspension.
(2) a certain amount of polymine (Polyethyleneimine, PEI) is joined above-mentioned g-C3N4In suspension, stir 1～3h, add the water of equivalent after being centrifuged and toppling over the supernatant, and be sufficiently stirred for, obtain CNP solution.
(3) take above-mentioned CNP solution, the sodium tetraphenylborate solution configured dropwise instilled in above-mentioned taken solution, and centrifugal after stirring 1～3h, gained solid is dried at a temperature of 60～80 DEG C 8～12 hours, both presoma.
(4) grinding of dried presoma is uniformly placed in crucible, it is placed in Muffle furnace and calcines at air atmosphere, calcining heat is 500 DEG C～520 DEG C of heating rates are 1 DEG C/min～5 DEG C/min, natural cooling after being incubated 4 hours, gained powder is nonmetal liquid phase doping and modifies the B doping g-C obtained3N4Photocatalyst.
In step (1), described g-C3N4Being prepared by carbamide 550 DEG C of calcinings in atmosphere, calcining heating rate is 10 DEG C/min.Preferably m (g-C3N4): v (H2O)=10mg:1ml.
In step (2), preferably m (g-C3N4): m (PEI)=10:1.
In step (3), the concentration of sodium tetraphenylborate solution is 1mg/ml, sodium tetraphenylborate solution: g-C3N4Than being (20-110) ml:0.2g, preferably 70ml:0.2g.
The B doping g-C prepared according to the nonmetal liquid phase doping of the inventive method gained3N4Photocatalyst.The g-C that nonmetal liquid phase doping prepared by the inventive method is modified3N4Photocatalyst is used for photocatalysis solar energy.
The present invention selects cheap industrial chemicals carbamide to be presoma, with sodium tetraphenylborate as doped source, with polymine (Polyethyleneimine, PEI) it is surface charge modifying dose, use and be simply pyrolyzed polymerization, be successfully prepared and there is visible light-responded (> 420nm), organic polymer semiconductor material boron doped carboritride (the B-doped g-C that thermally-stabilised and chemical stability is superior3N4), with pure g-C3N4Compare, this material has the organizational structure pattern (having more mesoporous quantity) of novelty, hydrogen manufacturing characteristic shows advantageous characteristic, under a small amount of promoter and sacrifice agent participate in, it is thus achieved that hydrogen-producing speed 4280 μm ol h faster under sunlight-1/ g, is realized with a low cost photocatalysis solar energy conversion new forms of energy, has the highest application prospect.
Liquid phase doping is better than solid phase mechanical doping, wherein by g-C3N4Nonmetal liquid phase B doping and modification modified, mesoporous quantity can be improved, suppress g-C3N4Light induced electron and hole compound, improve g-C3N4Photocatalytic activity, these advantages make g-C3N4In the application great potential of photocatalysis and photodissociation hydrogen preparation field, simultaneously to g-C3N4Industrial applications important in inhibiting.The most nonmetal liquid phase doping modification g-C3N4The preparation of photocatalyst has great importance.
Accompanying drawing illustrates:
The pure g-C of Fig. 13N4And embodiment 2, the X-ray diffraction curve of example 4 product, wherein a is pure g-C3N4X-ray diffraction curve, b, c are respectively embodiment 2, the X-ray diffraction curve of example 4 product.
The pure g-C of Fig. 23N4And the scanning electron microscope image of embodiment 3 product, wherein a, b, c are pure g-C3N4Surface sweeping sem image, d, e, f are the scanning electron microscope image of embodiment 3 product.
The images of transmissive electron microscope of the CNPB-3 sample of preparation in Fig. 3 embodiment 3.
Fig. 4 embodiment (1～3) product infrared spectrum curve, wherein a is the infrared spectrum curve of embodiment 1 product, and b is the infrared spectrum curve of embodiment 2 product, and c is the infrared spectrum curve of embodiment 3 product.
The X-ray photoelectron spectroscopic analysis figure of Fig. 5 embodiment 3 product
The pure g-C of Fig. 63N4And the fluorescence spectrum that embodiment 2,3 product is under 400nm light excites.
The curve chart of Fig. 7 embodiment (1～4) Photocatalyzed Hydrogen Production amount.
Fig. 8 embodiment (1～4) Photocatalyzed Hydrogen Production speed bar diagram.
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 example.
Embodiment 1:
Accurately weigh the g-C of 2g3N4It is placed in the distilled water of 200ml after ultrasonic 0.5h, continues stirring 12h so that it is be sufficiently mixed, obtain g-C3N4Suspension.The PEI accurately weighing 0.2g joins above-mentioned g-C3N4In suspension, stir 1h, centrifugal and add a certain amount of water after toppling over the supernatant to 200ml, and be sufficiently stirred for, obtain CNP solution.Taking the CNP solution of 20ml, the sodium tetraphenylborate solution of the 1mg/ml configured by 20ml dropwise instills in above-mentioned taken solution, centrifugal after stirring 1h, is dried by gained solid 8 hours, had both obtained presoma at a temperature of 60 DEG C.Being ground by dried presoma and be uniformly placed in crucible, be placed in Muffle furnace and calcine at air atmosphere, calcining heat is 500 DEG C, and heating rate is 5 DEG C/min, natural cooling after being incubated 4 hours, and gained powder is the g-C of nonmetal liquid phase B doping and modification3N4Photocatalyst, is designated as CNPB-1.Take this catalyst 50mg, the deionized water of 90ml, the triethanolamine of 10ml (10vol.%) does sacrifice agent, 4mg chloroplatinic acid (Pt of 3wt.%) makees promoter, join altogether in reactor, the 300WXe lamp carrying 420nm optical filter is used to circulate in system for producing hydrogen and carry out Photocatalyzed Hydrogen Production experiment as visible light source, the glass using gas chromatography luxuriant and rich with fragrance Lay on the berth airtight, record hydrogen output curve such as the CNPB-1 line in Fig. 7.
Embodiment 2:
Accurately weigh the g-C of 2g3N4It is placed in the distilled water of 200ml after ultrasonic 1h, continues stirring 12h so that it is be sufficiently mixed, obtain g-C3N4Suspension.The PEI accurately weighing 0.2g joins above-mentioned g-C3N4In suspension, stir 2h, centrifugal and add a certain amount of water after toppling over the supernatant to 200ml, and be sufficiently stirred for, obtain CNP solution.Taking the CNP solution of 20ml, the sodium tetraphenylborate solution of the 1mg/ml configured by 50ml dropwise instills in above-mentioned taken solution, centrifugal after stirring 2h, is dried by gained solid 12 hours, had both obtained presoma at a temperature of 60 DEG C.Being ground by dried presoma and be uniformly placed in crucible, be placed in Muffle furnace stove and calcine at air atmosphere, calcining heat is 520 DEG C, and heating rate is 1 DEG C/min, natural cooling after being incubated 4 hours, and gained powder is the g-C of nonmetal liquid phase B doping and modification3N4Photocatalyst, is designated as CNPB-2.Take this catalyst 50mg, the deionized water of 90ml, the triethanolamine of 10ml (10vol.%) does sacrifice agent, 4mg chloroplatinic acid (Pt of 3wt.%) makees promoter, join altogether in reactor, the 300WXe lamp carrying 420nm optical filter is used to circulate in system for producing hydrogen and carry out Photocatalyzed Hydrogen Production experiment as visible light source, the glass using gas chromatography luxuriant and rich with fragrance Lay on the berth airtight, record hydrogen output curve such as the CNPB-2 line in Fig. 7.
Embodiment 3:
Accurately weigh the g-C of 2g3N4It is placed in the distilled water of 200ml after ultrasonic 2h, continues stirring 24h so that it is be sufficiently mixed, obtain g-C3N4Suspension.The PEI accurately weighing 0.2g joins above-mentioned g-C3N4In suspension, stir 3h, centrifugal and add a certain amount of water after toppling over the supernatant to 200ml, and be sufficiently stirred for, obtain CNP solution.Taking the CNP solution of 20ml, the sodium tetraphenylborate solution of the 1mg/ml configured by 70ml dropwise instills in above-mentioned taken solution, centrifugal after stirring 2h, is dried by gained solid 8 hours, had both obtained presoma at a temperature of 80 DEG C.Being ground by dried presoma and be uniformly placed in crucible, be placed in Muffle furnace stove and calcine at air atmosphere, calcining heat is 500 DEG C, and heating rate is 1 DEG C/min, natural cooling after being incubated 4 hours, and gained powder is the g-C of nonmetal liquid phase B doping and modification3N4Photocatalyst, is designated as CNPB-3.Take this catalyst 50mg, the deionized water of 90ml, the triethanolamine of 10ml (10vol.%) does sacrifice agent, 4mg chloroplatinic acid (Pt of 3wt.%) makees promoter, join altogether in reactor, the 300WXe lamp carrying 420nm optical filter is used to circulate in system for producing hydrogen and carry out Photocatalyzed Hydrogen Production experiment as visible light source, the glass using gas chromatography luxuriant and rich with fragrance Lay on the berth airtight, record hydrogen output curve such as the CNPB-3 line in Fig. 7.
Embodiment 4:
Accurately weigh the g-C of 2g3N4It is placed in the distilled water of 200ml after ultrasonic 2h, continues stirring 24h so that it is be sufficiently mixed, obtain g-C3N4Suspension.The PEI accurately weighing 0.2g joins above-mentioned g-C3N4In suspension, stir 3h, centrifugal and add a certain amount of water after toppling over the supernatant to 200ml, and be sufficiently stirred for, obtain CNP solution.Taking the CNP solution of 20ml, the sodium tetraphenylborate solution of the 1mg/ml configured by 110ml dropwise instills in above-mentioned taken solution, centrifugal after stirring 3h, is dried by gained solid 12 hours, had both obtained presoma at a temperature of 80 DEG C.Being ground by dried presoma and be uniformly placed in crucible, be placed in Muffle furnace stove and calcine at air atmosphere, calcining heat is 500 DEG C, and heating rate is 5 DEG C/min, natural cooling after being incubated 4 hours, and gained powder is the g-C of nonmetal liquid phase B doping and modification3N4Photocatalyst, is designated as CNPB-4.Take this catalyst 50mg, the deionized water of 90ml, the triethanolamine of 10ml (10vol.%) does sacrifice agent, 4mg chloroplatinic acid (Pt of 3wt.%) makees promoter, join altogether in reactor, the 300WXe lamp carrying 420nm optical filter is used to circulate in system for producing hydrogen and carry out Photocatalyzed Hydrogen Production experiment as visible light source, the glass using gas chromatography luxuriant and rich with fragrance Lay on the berth airtight, record hydrogen output curve such as the CNPB-4 line in Fig. 7.
Note: CNUB-JX sample as a comparison, for the optimum sample of solid phase machinery B doping
Table 1 is that in embodiment, CNPB-X sample specific surface area, pore volume and the hydrogen-producing speed of preparation compare.
Claims (5)
1. a nonmetal liquid phase doping prepares B doping g-C3N4The method of photocatalyst, it is characterised in that comprise the following steps:
(1) by a certain amount of g-C3N4After being placed in distilled water ultrasonic 0.5～2h, continue stirring 12～24h so that it is be sufficiently mixed, obtain g-C3N4Suspension；
(2) a certain amount of polymine (Polyethyleneimine, PEI) is joined above-mentioned g-C3N4In suspension, stir 1～3h, add the water of equivalent after being centrifuged and toppling over the supernatant, and be sufficiently stirred for, obtain CNP solution；
(3) take above-mentioned CNP solution, the sodium tetraphenylborate solution configured dropwise is instilled in above-mentioned taken solution, and centrifugal after stirring 1～3h, gained solid is dried at a temperature of 60～80 DEG C 8～12 hours, obtains presoma；
(4) grinding of dried presoma is uniformly placed in crucible, it is placed in Muffle furnace and calcines at air atmosphere, calcining heat is 500 DEG C～520 DEG C of heating rates are 1 DEG C/min～5 DEG C/min, natural cooling after being incubated 4 hours, gained powder is nonmetal liquid phase doping and modifies the B doping g-C obtained3N4Photocatalyst；
In step (2), m (g-C3N4): m (PEI)=10:1；
The concentration of sodium tetraphenylborate solution is 1mg/mL, sodium tetraphenylborate solution: g-C3N4Than being (20-110) mL:0.2g.
2. according to the method for claim 1, it is characterised in that in step (1), described g-C3N4Being prepared by carbamide 550 DEG C of calcinings in atmosphere, calcining heating rate is 10 DEG C/min.
3. according to the method for claim 1, it is characterised in that in step (1), m (g-C3N4): V (H2O)=10mg:1mL.
4. according to the either method gained B doping g-C of claim 1-33N4Photocatalyst.
5. according to the either method gained B doping g-C of claim 1-33N4Photocatalyst for photocatalysis hydrogen production.
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| CN107649165A (en) * | 2017-10-20 | 2018-02-02 | 秦永泽 | Photocatalysis film and preparation method in a kind of foam metal graphene compound substrate |
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| CN110433844B (en) * | 2019-08-08 | 2022-04-08 | 盐城工学院 | Be used for high-efficient processing to contain Cr6+(B, O) Co-doping of waste Water with g-C3N4Method for preparing photocatalyst |
| CN110813345B (en) * | 2019-08-16 | 2022-04-15 | 济南大学 | Method for preparing novel carbon-nitrogen nonmetal photocatalyst by utilizing p/n junction principle |
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| CN113680364B (en) * | 2021-08-26 | 2023-09-29 | 吉林师范大学 | Meta-aminophenylboronic acid doped graphite-phase carbon nitride photocatalyst, preparation method and application thereof |
| CN115318323B (en) * | 2022-07-27 | 2023-11-21 | 天津大学（青岛）海洋工程研究院有限公司 | Cobalt phosphide-phosphorus loaded boron doped carbon nitride photocatalyst, preparation method and application |
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