CN103623856B - Spherical mesoporous carbon nitride photocatalyst with multistage nano structure - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
The invention discloses a spherical mesoporous carbon nitride photocatalyst with a multistage nano structure and a preparation method and application thereof and belongs to the technical field of material preparation and photocatalysis. The spherical mesoporous carbon nitride photocatalyst with the multistage nano structure is prepared by using cyanamide as a precursor, using spherical mesoporous silicon dioxide with a highly open structure as a hard template, carrying out thermal thermal polymerization and removing the hard template. The spherical mesoporous carbon nitride prepared by the preparation method has the characteristic that nanosheet or nanosheet-like small particles are uniformly diffused around from the sphere center to form a spherical micro nano structure of which the surface structure is highly open; compared with conventional bulk phase carbon nitride, the spherical mesoporous carbon nitride photocatalyst can obviously improve the specific surface area and the mass transfer effect and has efficient photocatalytic hydrogen production performance in the visible light. The spherical mesoporous carbon nitride photocatalyst adopts a simple synthetic process, has high catalysis efficiency and has wide application prospect in the field of catalysis/photocatalysis.
Description
Technical field
The invention belongs to material preparation and light-catalysed technical field, spherical mesoporous carbon nitride photocatalyst being specifically related to a kind of multi-level nano-structure and its preparation method and application.
Background technology
The energy is the material base of mankind's activity, and the development of human society be unable to do without the application and development of high-grade energy.Photocatalitic Technique of Semiconductor, drives chemical reaction, as photocatalytic hydrogen production by water decomposition (Chem. Rev. 2010,110,6503), CO by utilizing sunshine
2fixing reduction (Chem. Rev. 2001,101,953), selective oxidation operation reduction reaction, contaminant degradation and mineralising (Chem. Rev. 1995,95,69) etc., low-density solar energy is converted into highdensity chemical energy, has broad application prospects in the solution energy and environmental problem.Current people have synthesized hundreds of catalysis material, classify from the attribute of material, mainly contain inorganic semiconductor photochemical catalyst and organic semiconductor photochemical catalyst (Chem. Rev. 2012,112,1710).
Recently, high stability for chemical constitution organic polymer semiconductor-graphite phase carbon nitride is incorporated into photocatalysis research field by king etc., for photodissociation aquatic products hydrogen, produces oxygen (Nat. Mater. 2009,8,76), causes the extensive concern of people.But body phase carbon nitride exists the crucial scientific and technical difficult problems such as solar energy utilization ratio is low, photo-generated carrier compound is serious, quantum efficiency is low, constrain its large-scale promotion application in photocatalysis field.Nanometer technology has unique skin effect, small-size effect and quantum size effect, and the synergy of these effects will significantly improve the photocatalysis performance of nano material.Therefore, nano functionalization semiconductor light-catalyst effectively can overcome the shortcoming of body phase semi-conducting material, promotes the carrying out of light-catalyzed reaction.Recently, people mainly adopt traditional hard template method to prepare mesoporousization azotized carbon nano photochemical catalyst, the physicochemical property of optimization of catalysts is set about from the surface topography aspect of material, effectively improve its photocatalysis efficiency, as: unordered mesoporous carbonitride (J. Am. Chem. Soc. 2009,131,1680), the order mesoporous carbonitride of SBA-15 type (Chem. Mater. 2009,21,4093; Adv. Funct. Mater. 2013,23,3008), azotized carbon nano rod (Chem. Mater. 2011,23,4344) and nanometer sheet (Adv. Funct. Mater. 2012,22,4763), hollow spheres carbonitride (Nature Communications 2012,3,1139) etc., the development of carbon nitride photocatalyst is effectively promoted.But, the surface texture of these traditional mesoporous azotized carbon nano materials also relatively " closing " at present, effectively can not promote that the mass transfer of reaction substrate in nano pore spreads, be difficult to give full play to the special physicochemical property of polymer semiconductor, reach that to overcome photo-generated carrier mobility in polymer semiconductor low, the object of the shortcomings such as compound is serious.The hollow spheres carbonitride that such as photocatalytic water usefulness is the highest at present, the nano pore on its wall can cave in when removing template, hinders the chemical reaction on inner surface, thus is unfavorable for efficiently carrying out of light-catalyzed reaction.Therefore, optimize the preparation technology that azotized carbon nano light urges agent, find suitable template and construct surface texture height and " open wide " and the few nanometer hierarchical structure of body phase defect, become an important topic of urging agent to study when azotized carbon nano light.
Summary of the invention
Spherical mesoporous carbon nitride photocatalyst that the object of the present invention is to provide a kind of multi-level nano-structure and its preparation method and application.Catalyst prepared by the present invention has evenly to be dispersed to surrounding by the centre of sphere with the granule of nanometer sheet or similar nanometer sheet, form that surface texture height " opens wide ", that structure height is stable spherical micro-nano-structure, significantly can improve the mass transfer diffusion process in multiphase photocatalysis reaction and the quick separating and the interfacial migration that promote photo-generated carrier, realize efficient visible light photocatalytic water and produce hydrogen.Present invention process is simple, and catalytic efficiency is high, has broad application prospects in photocatalysis field.
For achieving the above object, the present invention adopts following technical scheme:
The spherical mesoporous carbon nitride photocatalyst of multi-level nano-structure is have the unlimited spherical mesoporous carbonitride of multistage surface texture height, and belong to organic polymer semiconductor, chemical formula is C
3n
4, there are 100 ~ 250 m
2the high-specific surface area of/g, light absorption band edge, at 400 ~ 500 nm, has efficient Photocatalyzed Hydrogen Production performance under visible light.
The method preparing the spherical mesoporous carbon nitride photocatalyst of multi-level nano-structure as above takes the spherical mesoporous silica template agent KCC-1 that surface topography and nanostructured open wide, the presoma cyanamide of melting is injected in template, after high temperature thermopolymerization, after removing template, namely obtain evenly being dispersed to surrounding by the centre of sphere with the granule of nanometer sheet or similar nanometer sheet forming the spherical mesoporous carbonitride that surface texture height opens wide, nanostructure height is stable.Described preparation method comprises the following steps:
(1) the spherical mesoporous silica template agent KCC-1(Angew. Chem. Int. Ed. 2010,49,9652 that opens wide of synthetic surface pattern and nanostructured).The amylalcohol of 1.5 ~ 4.0g tetraethyl orthosilicate (TEOS) and 1.0 ~ 3.0mL is dissolved into wiring solution-forming A in 30mL cyclohexane; 0.5 ~ 2.0g bromide sixteen alkyls pyridine (CPB) and 0.5 ~ 1.0g urea are dissolved into wiring solution-forming B in 30mL water.By A, B two parts of solution mix and blends, and move in microwave reaction kettle, 373 ~ 413K heating using microwave, 1 ~ 6h.React rear water and acetone centrifuge washing, dry, and 723 ~ 923K calcines 4 ~ 8h in Muffle furnace, obtains the agent of KCC-1 silica template.
(2) by template as in 0.5 ~ 2 mol/L HCl, 353K closes stirring 12 ~ 24h, carries out acid treatment to template.Centrifugal, dry, grinding.
(3) containing in the round-bottomed flask of suction filtration head, add KCC-1 and the cyanamide of the step (2) that mass ratio is 1:4 ~ 1:10, under vacuum, " ultrasonic+heating " process 2 ~ 6h, adds 10 ~ 20mL and washes centrifugal, dry, grinding.By pressed powder high-temperature calcination 2 ~ 10h in 723 ~ 923K nitrogen furnace.After high temperature thermopolymerization, add 4 mol/L NH
4hF
2solution etches removing silica template, washing, dries, obtains spherical mesoporous carbonitride.
The spherical mesoporous carbon nitride photocatalyst of described multi-level nano-structure can be applicable to decomposition water hydrogen making under visible ray, and its hydrogen-producing speed increases significantly relative to conventional bulk phase carbon nitride.
Remarkable advantage of the present invention is: the spherical mesoporous silica KCC-1 opened wide with surface topography and nanostructured is for hard mould agent, adopt " surperficial acidifying " and " vacuum-ultrasonic-heating " combination technique, synthesize the spherical mesoporous carbonitride of the multi-level nano-structure that microcosmic surface height " opens wide ", remarkable quick separating and the interfacial migration improving the mass transfer diffusion process in multiphase photocatalysis reaction and promote photo-generated carrier, thus make its visible ray photodissociation aquatic products hydrogen activity have significant raising compared with body phase carbon nitride.This catalyst not containing metal element simultaneously, has synthesis technique simple, and catalyst stability is high, nontoxic, be easy to the features such as recycle and reuse, realistic need of production, has very high practical value and wide application prospect.
Accompanying drawing explanation
Fig. 1 is that the high-resolution-ration transmission electric-lens HTEM of the spherical mesoporous carbonitride a of the multi-level nano-structure of embodiment 3 gained schemes.
Fig. 2 is the Performance comparision figure that the spherical mesoporous carbonitride a of the multi-level nano-structure of embodiment 3 gained and traditional body phase carbon nitride b carry out visible light catalytic decomposition water hydrogen making.
Detailed description of the invention
Be below several embodiments of the present invention, further illustrate the present invention, but the present invention is not limited only to this.
embodiment 1
The amylalcohol of 2.5g tetraethyl orthosilicate (TEOS) and 3.0mL is dissolved into wiring solution-forming A in 30mL cyclohexane; 1.0g bromide sixteen alkyls pyridine (CPB) and 0.8g urea are dissolved into wiring solution-forming B in 30mL water.By A, B two parts of solution mix and blends, and move in microwave reaction kettle, 413K heating using microwave 4h.React rear water and acetone centrifuge washing, dry, and 923K calcines 4h in Muffle furnace, obtains the agent of KCC-1 silica template.By in template as in 1.0mol/LHCl, 353K close stir 24h, acid treatment is carried out to template.Centrifugal, dry, grinding.Containing in the round-bottomed flask of suction filtration head, add KCC-1 and the cyanamide of the step (2) that mass ratio is 1:9, under vacuum (<1KPa) condition, " ultrasonic+heating (328K) " process 6h, adds 20mL and washes centrifugal, dry, grinding.By pressed powder high-temperature calcination 3h in 873K nitrogen furnace.After high temperature thermopolymerization, add 4 mol/L NH
4hF
2aqueous solution etching removing silica template, washing, dries, the spherical mesoporous carbonitride of obtained multi-level nano-structure.
embodiment 2
The amylalcohol of 3.0g tetraethyl orthosilicate (TEOS) and 2.0mL is dissolved into wiring solution-forming A in 30mL cyclohexane; 2.0g bromide sixteen alkyls pyridine (CPB) and 1.0g urea are dissolved into wiring solution-forming B in 30mL water.By A, B two parts of solution mix and blends, and move in microwave reaction kettle, 393K heating using microwave 6h.React rear water and acetone centrifuge washing, dry, and 873K calcines 8h in Muffle furnace, obtains the agent of KCC-1 silica template.By in template as in 2.0mol/LHCl, 353K close stir 12h, acid treatment is carried out to template.Centrifugal, dry, grinding.Containing in the round-bottomed flask of suction filtration head, add KCC-1 and the cyanamide of the step (2) that mass ratio is 1:5, under vacuum (<1KPa) condition, " ultrasonic+heating (333K) " process 6h, adds 10mL and washes centrifugal, dry, grinding.By pressed powder high-temperature calcination 10h in 773K nitrogen furnace.After high temperature thermopolymerization, add 4 mol/L NH
4hF
2aqueous solution etching removing silica template, washing, dries, the spherical mesoporous carbonitride of obtained multi-level nano-structure.
embodiment 3
The amylalcohol of 2.5g tetraethyl orthosilicate (TEOS) and 1.5mL is dissolved into wiring solution-forming A in 30mL cyclohexane; 1.0g bromide sixteen alkyls pyridine (CPB) and 0.6g urea are dissolved into wiring solution-forming B in 30mL water.By A, B two parts of solution mix and blends, and move in microwave reaction kettle, 393K heating using microwave 2h.React rear water and acetone centrifuge washing, dry, and 823K calcines 6h in Muffle furnace, obtains the agent of KCC-1 silica template.By in template as in 1.0mol/LHCl, 353K close stir 24h, acid treatment is carried out to template.Centrifugal, dry, grinding.Containing in the round-bottomed flask of suction filtration head, add KCC-1 and the cyanamide of the step (2) that mass ratio is 1:8, under vacuum (<1KPa) condition, " ultrasonic+heating (328K) " process 4h, adds 15mL and washes centrifugal, dry, grinding.By pressed powder high-temperature calcination 4h in 823K nitrogen furnace.After high temperature thermopolymerization, add 4 mol/L NH
4hF
2aqueous solution etching removing silica template, washing, dries, the spherical mesoporous carbonitride of obtained multi-level nano-structure.
embodiment 4
The amylalcohol of 2.5g tetraethyl orthosilicate (TEOS) and 1.0mL is dissolved into wiring solution-forming A in 30mL cyclohexane; 1.0g bromide sixteen alkyls pyridine (CPB) and 0.7g urea are dissolved into wiring solution-forming B in 30mL water.By A, B two parts of solution mix and blends, and move in microwave reaction kettle, 383K heating using microwave 6h.React rear water and acetone centrifuge washing, dry, and 773K calcines 8h in Muffle furnace, obtains the agent of KCC-1 silica template.By in template as in 0.5mol/LHCl, 353K close stir 24h, acid treatment is carried out to template.Centrifugal, dry, grinding.Containing in the round-bottomed flask of suction filtration head, add KCC-1 and the cyanamide of the step (2) that mass ratio is 1:8, under vacuum (<1KPa) condition, " ultrasonic+heating (333K) " process 4h, adds 20mL and washes centrifugal, dry, grinding.By pressed powder high-temperature calcination 2h in 923K nitrogen furnace.After high temperature thermopolymerization, add 4 mol/L NH
4hF
2aqueous solution etching removing silica template, washing, dries, the spherical mesoporous carbonitride of obtained multi-level nano-structure.
embodiment 5
The amylalcohol of 1.5g tetraethyl orthosilicate (TEOS) and 1.0mL is dissolved into wiring solution-forming A in 30mL cyclohexane; 0.5g bromide sixteen alkyls pyridine (CPB) and 0.5g urea are dissolved into wiring solution-forming B in 30mL water.By A, B two parts of solution mix and blends, and move in microwave reaction kettle, 373K heating using microwave 4h.React rear water and acetone centrifuge washing, dry, and 823K calcines 6h in Muffle furnace, obtains the agent of KCC-1 silica template.By in template as in 1.0mol/LHCl, 353K close stir 18h, acid treatment is carried out to template.Centrifugal, dry, grinding.Containing in the round-bottomed flask of suction filtration head, add KCC-1 and the cyanamide of the step (2) that mass ratio is 1:6, under vacuum (<1KPa) condition, " ultrasonic+heating (323K) " process 3h, adds 12mL and washes centrifugal, dry, grinding.By pressed powder high-temperature calcination 6h in 723K nitrogen furnace.After high temperature thermopolymerization, add 4 mol/L NH
4hF
2aqueous solution etching removing silica template, washing, dries, the spherical mesoporous carbonitride of obtained multi-level nano-structure.
Performance test
Fig. 1 is that the high-resolution-ration transmission electric-lens HTEM of the spherical mesoporous carbon nitride photocatalyst a of the multi-level nano-structure of embodiment 3 gained schemes.As can be seen from the figure, spherical mesoporous carbonitride diameter is about 250nm, and equably diffuses to form surface texture height by the centre of sphere to surrounding with the granule of nanometer sheet or similar nanometer sheet and open wide multistage layer structure.Respectively choose a region at the center and peripheral of ball, can find out that surperficial multistage lamellar structure is very clear as region " 1 " (Fig. 1 b) and region " 2 " (Fig. 1 c) carries out amplifying observation.
Fig. 2 is the spherical mesoporous carbon nitride photocatalyst a of the multi-level nano-structure of embodiment 3 gained and the Performance comparision figure of body phase carbon nitride b photochemical catalyzing hydrogen making.40mg catalyst and reaction reagent (containing the 100mL triethanolamine aqueous solution of 10 vol. %, original position photo-reduction H
2ptCl
6, i.e. 3 wt. % Pt) react in upper illuminated reactor.Can find that from figure the hydrogen-producing speed of the product (filter plate λ > 420 nm) under visible light prepared reaches 574 μm of ol/h, improve 45 times compared with body phase carbon nitride (12.5 μm of ol/h).Take turns through 4, after the continuous illumination of 20h, spherical mesoporous carbonitride a still keeps very high activity stability, does not occur obvious inactivation.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. a spherical mesoporous carbon nitride photocatalyst for multi-level nano-structure, is characterized in that: described spherical mesoporous carbonitride has and diffuses to form to surrounding the micro-nano structure that surface texture opens wide, nanostructure height is stable by the centre of sphere equably with the granule of nanometer sheet or similar nanometer sheet; Described spherical mesoporous carbonitride, has 100 ~ 250 m
2the high-specific surface area of/g, light absorption band edge is at 400-500 nm.
2. the spherical mesoporous carbon nitride photocatalyst of multi-level nano-structure according to claim 1, is characterized in that: the chemical formula of carbonitride is C
3n
4, be a kind of organic polymer semiconductor.
3. prepare the method for the spherical mesoporous carbon nitride photocatalyst of multi-level nano-structure as claimed in claim 1 for one kind, it is characterized in that: take cyanamide as predecessor and spherical mesoporous silica KCC-1 be hard template, carry out high temperature thermopolymerization, after removing hard template, obtain spherical mesoporous carbonitride.
4. the preparation method of the spherical mesoporous carbon nitride photocatalyst of multi-level nano-structure according to claim 3, is characterized in that: comprise the following steps:
(1) the spherical mesoporous silica template agent KCC-1 that opens wide of synthetic surface pattern and nanostructured;
(2) by spherical mesoporous silica KCC-1 after high-temperature calcination removing organic matter, grinding, adds watery hydrochloric acid under thermal agitation and carries out acid treatment adding, centrifugal, dries, grinding;
(3) containing in the flask of suction filtration head, silica and the cyanamide of the step (2) that mass ratio is 1:4 ~ 1:10 is added, under vacuum, ultrasonic and heating; Add water the excessive cyanamide of centrifugal removing, dries; By pressed powder high-temperature calcination 2 ~ 8h in 723 ~ 923K nitrogen furnace; Use NH
4hF
2solution etches removing silica template, washing, dries, obtains spherical mesoporous carbonitride.
5. an application for the spherical mesoporous carbon nitride photocatalyst of multi-level nano-structure as claimed in claim 1, is characterized in that: the spherical mesoporous carbon nitride photocatalyst of described multi-level nano-structure is applied to decomposition water hydrogen making under visible ray.
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