CN103011099B - Spherical mesoporous carbon nitride material and preparation method thereof - Google Patents
Spherical mesoporous carbon nitride material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a spherical mesoporous C3N4 material with a hollow cavity nanostructure and a preparation method thereof. The preparation method comprises the following steps: modifying a nano solid SiO2 spherule to get a solid SiO2 material coated with mesoporous SiO2 on the outer layer, further adding alkali, selectively etching off the inner-layer solid SiO2 to get nano hollow mesoporous SiO2, fully impregnating the nano hollow mesoporous SiO2 in a water solution of a nitrogen-containing precursor, performing centrifugal drying, performing high-temperature roasting in protective gas, and then using hydrofluoric acid to dissolve the SiO2 to get the spherical hollow mesoporous nano C3N4. The prepared product has the specific surface area of 300-800m<2>/g and a cavity capable of loading other materials, is easy to perform mass transfer and can be further widely applied.
Description
Technical field
The invention belongs to field of material synthesis technology, particularly the spherical mesoporous C of one
3n
4material and preparation method thereof.
Background technology
Carbonitride is (C
3n
4) a kind of according to Theoretical Calculation and the mineral compound of synthetic.1989, Cohen and Liu went out β-C3N4 according to the structure design of known β-Si3N4, and the Young's modulus of β-C3N4 is about 410Gpa as calculated, close with adamantine Young's modulus.1996, Teter and Hemley was to C
3n
4re-start calculating, infer C
3n
45 kinds of structures may be had, i.e. α phase, β phase, Emission in Cubic, accurate Emission in Cubic and class graphite-phase.At ambient temperature, graphite-like structure carbonitride (g-C
3n
4) the most stable.G-C
3n
4have the laminate structure of similar graphite, interlayer contains C
3n
3ring or C
6n
7ring, is connected by the atom N of end between ring and forms the plane of one deck infinite expanding.
In recent years, g-C
3n
4due to the characteristic of semiconductor that it is special, and high hydrothermal stability and nontoxic, easily the feature such as preparation, is applied in catalyzed reaction by as novel non-metallic catalyst.Such as, (1) organic reaction, can directly as linked reaction, Fu-Ke reaction, Knoenenagel condensation reaction, alkene and the reaction of stable hydrocarbon cycloalkanes oxidation, alcohol oxidation reaction, CO
2the catalyzer of priming reaction, also can be used as the carrier of the catalysts such as selective hydrogenation; (2) photodegradation organic pollutant and photolysis water hydrogen.G-C
3n
4spectral bandwidth 2.7eV, have absorption in visible region, far away higher than the theoretical decomposition value of water.(3) electrocatalytic reaction.G-C
3n
4upper containing a large amount of pyridine nitrogen be proved to be to fuel cell cathodic reaction---oxygen reduction reaction (ORR) has very strong electrocatalysis.Be used as the g-C of above-mentioned catalyzer at present
3n
4material is mainly film, body phase or macropore, mesoporous material, but these materials to there is specific surface area too low, only have 30 ~ 100m
2/ g, or be unfavorable for the defect such as mass transfer or porosity difference, limit its catalytic performance.Nanometer spherical hollow material because have large specific surface area, can load other materials cavity, be easy to the advantages such as mass transfer, then can solve the defect of above-mentioned materials.
Current synthesis g-C
3n
4method mainly contain scorification, soft template method, although the spherical solid g-C of nanometer
3n
4can be prepared by scorification, but be difficult to use for reference nanometer spherical hollow g-C
3n
4preparation; Soft template method take mainly tensio-active agent as template, and nitrogen-containing precursor can prepare the body phase material with meso-hole structure through hydro-thermal reaction, but is difficult to directly obtain nanometer spherical hollow g-C
3n
4;
Summary of the invention:
Technical problem to be solved by this invention is: g-C of the prior art
3n
4material, exists that specific surface area is little, the defect of porosity difference, limits its catalytic performance,
For solving this technical problem, the present invention proposes with spherical hollow meso-porous nano SiO
2for hard mould agent prepares nanometer spherical hollow g-C
3n
4, the technical solution used in the present invention is:
The invention provides a kind of spherical mesoporous C with hollow cavity nanostructure
3n
4material, this spherical mesoporous C
3n
4in material, the size of nanoparticle is 100 ~ 200 nanometers, and the diameter of hollow cavity is 20 ~ 100nm, and the aperture of mesopore orbit is 2 ~ 10nm, and specific surface area is 300 ~ 800m
2/ g.
Present invention also offers a kind of above-mentioned spherical mesoporous C
3n
4the preparation method of material, concrete steps are:
(1) 2 ~ 10mL silicon source is dissolved in the mixed solvent of 50 ~ 100mL ethanol and 5 ~ 20mL water, the saturated strong aqua of agitation and dropping 1 ~ 10mL, continues stirring 1 ~ 5h, filter, dry, obtain intermediate product A;
As preferably: silicon source is selected from the aqueous solution of pure tetraethyl orthosilicate TEOS, the silicon sol of 0.1 ~ 0.5mol/L or the water glass of 0.1 ~ 0.5mol/L;
(2) the intermediate product A obtained in 0.5g step (1) is scattered in 50 ~ 150mL water, add containing 0.2 ~ 1g cats product, 100 ~ 300mL ethanol, 100 ~ 300mL water, the mixed solution of the saturated strong aqua of 1 ~ 10mL, stir 30min, drip 0.5 ~ 5mL silicon source, after continuing stirring 3 ~ 9h, filter, drying, obtains intermediate product B;
As preferably: cats product refers to cetyl trimethylammonium bromide CTAB or palmityl trimethyl ammonium chloride CTAC,
This step is by solid for nanometer SiO
2bead (intermediate product A), through modification, obtains outer mesoporous SiO
2the solid SiO of coated nanometer
2material (intermediate product B);
(3) be dissolved in 100mL water by 0.1 ~ 1g alkali, and add the product B that step (2) obtains, 20 ~ 50 DEG C are stirred 6h, filter, dry, and the tensio-active agent then in atmosphere in roasting removing product, obtains intermediate product C;
As preferably: alkali is selected from NaHCO
3, Na
2cO
3or NaOH,
This step is by adding alkali, and selective etch falls the solid SiO of internal layer
2, obtain the mesoporous SiO of hollow nano
2(intermediate product C);
(4) the intermediate product C that 1g step (3) obtains is got, joining concentration is that the nitrogen-containing precursor aqueous solution 10mL of 0.1-0.5g/mL fully floods, after centrifugal drying, by product at temperature 500 ~ 800 DEG C, roasting in nitrogen or argon atmospher, then with saturated hydrofluoric acid dissolution SiO
2obtain spherical hollow meso-porous nano C
3n
4,
As preferably: nitrogen-containing precursor is selected from cyanamide, Dyhard RU 100 or trimeric cyanamide.
The invention has the beneficial effects as follows: the present invention is first by solid for nanometer SiO
2bead makes the mesoporous SiO of hollow nano by modification
2, then add nitrogen-containing precursor thermal condensation, prepare the spherical C with hollow meso-porous nano structure
3n
4, preparation process is simple, does not need to add the organic solvents such as tetracol phenixin, can not cause environmental pollution.Prepared product has 300 ~ 800m
2the specific surface area of/g, can as the cavity of load other materials, be easy to mass transfer, be therefore more widely used.
Accompanying drawing explanation
Fig. 1: spherical hollow meso-porous nano C prepared by the present invention
3n
4tEM photo.
Embodiment
Embodiment (one)
The pure TEOS of 10mL joins in the mixing solutions of 100mL ethanol and 20mL water, and then add saturated strong aqua 10mL, mixture is rapid stirring at room temperature, obtains white SiO
2soliquid, centrifugal, water and washing with alcohol, dry, obtain the solid SiO that median size is 80nm
2bead, i.e. intermediate product A.
Getting above-mentioned median size is the solid SiO of 80nm
2bead 0.5g, add water 150mL, ultrasonic 15min, then adds cetyl trimethylammonium bromide (CTAB) 1.0g, water 300mL, ethanol 300mL, saturated strong aqua 10mL, stirs half an hour, then add pure TEOS5mL, continue to stir 6h, product is centrifugal obtains intermediate product B; Product B is scattered in the 100mL aqueous solution again, at 50 DEG C, under vigorous stirring, adds 1gNa
2cO
3, after stirring 10h, collected by centrifugation product, dry at 80 DEG C, be then placed in retort furnace, in air atmosphere, 550 DEG C of roasting 5h, obtain intermediate product C.
Get the aqueous solution of 10mL containing cyanamide 5g, flood above-mentioned intermediate product C and spend the night, centrifugal, abandon supernatant, 80 DEG C of dryings, are then placed in tube furnace, N
2in atmosphere, 600 DEG C of roasting 5h, are cooled to room temperature, and product 2M HF washs, and centrifugal drying obtains the mesoporous carbonitride of spherical hollow, and through XRD qualification, product is the mesoporous C of ball shaped nano hollow
3n
4; By TEM technology, obtain the mesoporous C of ball shaped nano hollow
3n
4in, the mean pore size of mesopore orbit is 5nm, and average hollow cavity diameter is 80nm, average specific surface area is 532m
2/ g.
Embodiment (two)
The TEOS that 2mL is pure joins in the mixing solutions of 50mL ethanol and 5mL water, and then add saturated strong aqua 1mL, mixture is rapid stirring at room temperature, obtains white SiO
2soliquid, centrifugal, water and washing with alcohol, dry, obtain the solid SiO that median size is 40nm
2bead, i.e. intermediate product A.
Get the solid SiO of above-mentioned 40nm
2bead 0.5g, add water 50mL, ultrasonic 15min, then adds palmityl trimethyl ammonium chloride (CTAB) 0.2g, water 100mL, ethanol 100mL, saturated strong aqua 1mL, stirs half an hour, then adds the sodium silicate solution 0.5mL of 0.5mol/L, continue to stir 6h, product is centrifugal obtains intermediate product B; Product B is scattered in the 100mL aqueous solution again, at 20 DEG C, under vigorous stirring, adds 0.1gNaHCO
3, after stirring 10h, collected by centrifugation product, dry at 80 DEG C, be then placed in retort furnace, in air atmosphere, 550 DEG C of roasting 5h, obtain intermediate product C.
Get the aqueous solution of 10mL containing Dyhard RU 100 1g, flood above-mentioned intermediate product C and spend the night, centrifugal, abandon supernatant, 80 DEG C of dryings, are then placed in tube furnace, in Ar atmosphere, 600 DEG C of roasting 5h, are cooled to room temperature, product 2M HF, 80 DEG C of washings, centrifugal drying, obtains the mesoporous carbonitride of spherical hollow, through XRD qualification, product is the mesoporous C of ball shaped nano hollow
3n
4; By TEM technology, obtain the mesoporous C of ball shaped nano hollow
3n
4in, the mean pore size of mesopore orbit is 3.5nm, and average hollow cavity diameter is 80nm, and average specific surface area is 628m
2/ g.
Embodiment (three)
The TEOS that 5mL is pure joins in the mixing solutions of 100mL ethanol and 30mL water, then adds KOH0.15g, and mixture is rapid stirring at room temperature, obtains white SiO
2soliquid, centrifugal, water and washing with alcohol, dry, obtain the solid SiO that median size is 60nm
2bead, i.e. intermediate product A.
Get the solid SiO of above-mentioned 60nm
2bead 0.5g, add water 100mL, ultrasonic 15min, then adds palmityl trimethyl ammonium chloride (CTAC) 0.75g, water 150mL, ethanol 150mL, saturated strong aqua 3mL, stirs half an hour, then add pure TEOS2mL, continue to stir 6h, product is centrifugal obtains intermediate product B; Again product B is scattered in the 100mL aqueous solution, at 50 DEG C, under vigorous stirring, adds 0.2g Na
2cO
3, after stirring 6h, collected by centrifugation product, dry at 80 DEG C, be then placed in retort furnace, in air atmosphere, 550 DEG C of roasting 5h, obtain intermediate product C.
Get the aqueous solution of 10mL containing cyanamide 3g, flood above-mentioned intermediate product C and spend the night, centrifugal, abandon supernatant, 80 DEG C of dryings, are then placed in tube furnace, N
2in atmosphere, 600 DEG C of roasting 5h, are cooled to room temperature, and product 2M HF washs, and centrifugal drying obtains the mesoporous carbonitride of spherical hollow, and through XRD qualification, product is the mesoporous C of ball shaped nano hollow
3n
4; By TEM technology, obtain the mesoporous C of ball shaped nano hollow
3n
4in, the mean pore size of mesopore orbit is 3nm, and average hollow cavity diameter is 60nm, and average specific surface area is 492m
2/ g.
Claims (3)
1. a spherical mesoporous C
3n
4the preparation method of material, is characterized in that: described spherical mesoporous C
3n
4material has hollow cavity nanostructure, spherical mesoporous C
3n
4in material, the size of nanoparticle is 100 ~ 200 nanometers, and the diameter of hollow cavity is 20 ~ 100nm, and the aperture of mesopore orbit is 2 ~ 10nm, and specific surface area is 300 ~ 800m
2/ g,
Described preparation method is,
(1) 2 ~ 10mL silicon source is dissolved in the mixed solvent of 50 ~ 100mL ethanol and 5 ~ 20mL water, the saturated strong aqua of agitation and dropping 1 ~ 10mL, continues stirring 1 ~ 5h, filters, dry, obtains intermediate product A;
(2) by the intermediate product A ultrasonic disperse that obtains in 0.5g step (1) in 50 ~ 150mL water, add containing 0.2 ~ 1g cats product, 100 ~ 300mL ethanol, 100 ~ 300mL water, the mixed solution of 1 ~ 10mL ammoniacal liquor, stir 30min, drip 0.5 ~ 5mL silicon source, after continuing stirring 3 ~ 9h, filter, drying, obtains intermediate product B
Wherein, described cats product refers to cetyl trimethylammonium bromide CTAB or palmityl trimethyl ammonium chloride CTAC;
(3) be dissolved in 100mL water by 0.1 ~ 1g alkali, and add the product B that step (2) obtains, 20 ~ 50 DEG C are stirred 6h, filter, dry, and the tensio-active agent then in atmosphere in roasting removing product, obtains intermediate product C,
Wherein, described alkali is NaHCO
3or Na
2cO
3;
(4) product C that 1g step (3) obtains is got, joining concentration is that the nitrogen-containing precursor aqueous solution 10mL of 0.1-0.5g/mL fully floods, after centrifugal drying, by product at temperature 500 ~ 800 DEG C, roasting in nitrogen or argon gas atmosphere, then use saturated hydrofluoric acid aqueous solution, dissolve SiO
2obtain spherical hollow meso-porous nano C
3n
4.
2. spherical mesoporous C as claimed in claim 1
3n
4the preparation method of material, is characterized in that: step (1) or the silicon source described in (2) are selected from the aqueous solution of pure tetraethyl orthosilicate TEOS, the silicon sol of 0.1 ~ 0.5mol/L or the water glass of 0.1 ~ 0.5mol/L.
3. spherical mesoporous C as claimed in claim 1
3n
4the preparation method of material, is characterized in that: the nitrogen-containing precursor described in step (4) is selected from cyanamide, Dyhard RU 100 or trimeric cyanamide.
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