A kind of method for preparing the composite semiconductor material with meso-hole structure
Technical field
The invention provides a kind of hard template to prepare the composite semiconductor (N-CeO with meso-hole structure2/mpg-C3N4)
Method, material prepared by this method not only have higher specific surface area, and N doping can be prepared in calcination process
CeO2, the composite semiconductor material achievable CO under simulated solar irradiation2To CH4, CO photocatalytic conversion.Belong to catalysis material
And technical field of nano material, it is related to the novel processing step based on the composite mesoporous semi-conducting material of class graphitic nitralloy carbon.
Background technology
Mesoporous material is enjoyed due to its high specific surface area, big pore volume, regulatable mesoscopic structure and aperture size
Concern.Many researchs show that particle size and pore size are all an important factor for determining mesoporous material application, especially
In absorption large biological molecule (enzyme, protein etc.) and it is related in the field of macromolecule catalytic reaction.
2009, Wang Xinchen et al. carbon nitride materials of the report synthesis with graphite-like structure simultaneously used it for light decomposition water
Produce in hydrogen reaction.The 2D materials due to high nitrogen content, superior chemistry and thermal stability, special electronic structure,
Cost low (being mainly made up of nitrogen, carbon), the extensive concern for preparing the features such as simple and causing people.In the last few years, g-C3N4Having
The fields such as the degraded of machine object light, oxygen reduction reaction are widely studied.But the g-C that dinectly bruning is prepared3N4The ratio table of material
Area is relatively low, and photo-generate electron-hole easily occurs compound and makes its photocatalysis efficiency step-down.In order to solve these problems, can use
Hard template method prepares the g-C with meso-hole structure3N4Material, improve its specific surface area;By preparing composite semiconductor light-catalyst
Migration and the effective rate of utilization of photo-generate electron-hole are improved, and then improves the catalytic activity of photochemical catalyst.
The environmental problem such as energy shortage and greenhouse effects is the two large problems that people face at present, in existing solution
In, by the method for photocatalytic conversion, at room temperature by CO2Being converted into HC etc. has the compound of higher chemical energy, can be achieved too
Sun can be to chemical transformation of energy.However, the catalyst reported before still has the problems such as catalytic activity is relatively low, therefore, need badly
Develop new catalyst system.
The present invention explores simple hard template method and prepares the composite semiconductor material with meso-hole structure, g-C3N4Presoma
Can be CeO2Abundant nitrogen source is provided, N doping in situ is realized in calcination process, one-step calcination method prepares the CeO of N doping2Material
Material, hard template is removed with etching method afterwards, obtains the N-CeO with meso-hole structure2/mpg-C3N4Composite semiconductor material.
The content of the invention
The N-CeO with meso-hole structure is prepared it is an object of the invention to provide a kind of2/mpg-C3N4Composite semiconductor material
Method, and use it for room temperature CO2Photocatalytic conversion.
Here, the present invention provides a kind of method for preparing the composite semiconductor material with meso-hole structure, including following step
Suddenly:Step 1) is by class graphitic nitralloy carbon matrix precursor, hard template SiO2Ball is dispersed in water, and 10~60 points are stirred at 25~50 DEG C
Clock, wherein, the mass ratio of the class graphitic nitralloy carbon matrix precursor and water is 1~20, the SiO2The mass ratio of ball and water is 0.1
~1, preferably 0.2~1;
Step 2) adds in Ce sources in the solution that step 1) obtains according to 0~2 mass ratio, is stirred at 25~50 DEG C
0.5~6 hour;
The solution evaporating water that step 3) obtains step 2), drying overnight, obtains mixture of powders;
Step 4) calcines the mixture of powders that step 3) obtains 1~4 hour at 300~600 DEG C, obtains yellowish toner
End;
The pale yellow powder that step 5) obtains step 4) removes hard template, centrifuges, and dries, obtains having meso-hole structure
Composite semiconductor material.
The present invention provides a kind of high-specific surface area N-CeO prepared with meso-hole structure2/mpg-C3N4Composite semiconductor light
The new method of catalyst.This method is with SiO2For hard template, with cerous nitrate, cerous chlorate, cerium acetylacetonate, carbonic acid are hydrated
At least one of cerium, cerous sulfate etc. are as Ce sources, in calcination process, g-C3N4Presoma be CeO2Nitrogen source is provided, realized in situ
N is adulterated.The catalyst being prepared has higher specific surface area.By adjusting presoma type, the ratio of reactant, calcining
Temperature and heating rate, realize the optimization design of catalyst.The composite semiconductor catalyst of this method synthesis can realize room temperature
Lower CO2Conversion to HC compounds, there is higher stability.Preparation is simple by the present invention, and method is novel, cost
It is low, efficiency high, in CO2The fields such as photocatalytic conversion show wide application prospect.
In the present invention, the carbon of class graphitic nitralloy described in step 1) soluble precursor is urea, single cyanogen ammonia, in dicyandiamide extremely
Few one kind.
It is preferred that hard template SiO described in step 1)2The particle diameter of ball is 4~12nm.
In the present invention, in step 2), in cerous nitrate, cerous chlorate, hydration cerium acetylacetonate, cerous carbonate, cerous sulfate
Selection at least one is used as Ce sources.
In the present invention, the temperature of evaporating water described in step 3) is 50~100 DEG C.
Also, the temperature of drying overnight described in step 3) is 50~80 DEG C.
It is preferred that the heating rate calcined described in step 4) is 2~10K min-1。
It is preferred that NH is used in step 5)4HF removes hard template.
In the present invention, the prepared composite semiconductor material specific surface area with meso-hole structure is 50~300m2g-1, hole
Hold for 0.5~2cm3g-1, aperture is 4~12nm.
Also, in the prepared composite semiconductor material with meso-hole structure, CeO2With polycrystalline structure.
Brief description of the drawings
Fig. 1 a and Fig. 1 b are the mesoporous N-CeO of the gained of embodiment 12/mpg-C3N4The scanning electron of composite semiconductor material shows
Micro mirror (SEM) photo;
Fig. 2 a are the mesoporous N-CeO of the gained of embodiment 12/mpg-C3N4The projection electron microscope of composite semiconductor material
(TEM) photo;
Fig. 2 b are the mesoporous N-CeO of the gained of embodiment 12/mpg-C3N4The high resolution electron microscopy of composite semiconductor material
(HRTEM) photo;
Fig. 3 a are the mesoporous N-CeO of the gained of embodiment 12/mpg-C3N4The N of composite semiconductor material2Adsorption/desorption isothermal is bent
Line;
Fig. 3 b are the mesoporous N-CeO2/mpg-C of the gained of embodiment 13N4The corresponding pore-size distribution of composite semiconductor material
Figure.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the present invention, be not intended to limit the present invention.
The invention provides a kind of method for preparing the composite semiconductor material with meso-hole structure.The composite semiconductor material
Material is synthesized by simple step hard template method.Described composite semiconductor material is with two-dimentional (2D) material structure feature and
Even pore distribution, material have high specific surface area and pore volume, are very beneficial for the diffusion and absorption of reactant molecule, such as
CO2、H2O and oil catalysate etc..And the composite semiconductor material prepared has the skeleton of hybrid inorganic-organic, in life
The fields such as thing, absorption, catalysis and separation are with a wide range of applications.The synthetic method of the present invention is simple and easy, and method is novel,
Cost is low, efficiency high.
The method of the present invention includes:
(1) by g-C3N4Presoma (urea, single cyanogen ammonia, dicyandiamide, melamine etc.) be dissolved in Ludox, 25~
Stirred 10~60 minutes at 50 DEG C, wherein, g-C3N4Presoma and water mass ratio be 1~20, Ludox is by SiO2Ball with
The mass ratio of 0.1~1 (preferably 0.2~1) is added to the water obtained;
(2) according to 0~2 (preferably>0 and≤2) Ce sources are dissolved in above-mentioned solution by mass ratio, are stirred at 25~50 DEG C
0.5~6 hour;
(3) evaporating water, afterwards drying overnight in an oven;
(4) calcining obtains pale yellow powder in Muffle furnace;
(5) NH is used after4HF is gone out hard template, and product is obtained after centrifugal drying.
Wherein, preferably, g-C in step (1)3N4Presoma can be g-C3N4Soluble precursor.Step
Suddenly Ce sources described in (2) are at least one of cerous nitrate, cerous chlorate, hydration cerium acetylacetonate, cerous carbonate, cerous sulfate.
Preferably, 50~100 DEG C of water temperature is evaporated described in step (3).
Preferably, the temperature of baking oven is 50~80 DEG C described in step (3).
Preferably, 300~600 DEG C of the calcining heat of Muffle furnace described in step (4), time are 1~4 hour.
Preferably, Muffle furnace heating rate described in step (4) is 2~10K min-1。
Preferably, the particle size for the hard template SiO2 that the composite semiconductor material is selected is 4~12nm.
Preferably, the composite semiconductor material 2D structural materials, specific surface area are 50~300m2g-1, pore volume
For 0.5~2cm3g-1, aperture is 4~12nm.
It is characteristic of the invention that:The present invention provides a kind of high-specific surface area N-CeO prepared with meso-hole structure2/mpg-
C3N4The new method of composite semiconductor light-catalyst.This method is with SiO2For hard template, in cerous nitrate, cerous chlorate, acetyl is hydrated
At least one is selected to be used as Ce sources in acetonation cerium, cerous carbonate, cerous sulfate etc., in calcination process, g-C3N4Presoma be CeO2
Nitrogen source is provided, realizes N doping in situ.The catalyst being prepared has higher specific surface area.By adjust presoma type,
Ratio, calcining heat and the heating rate of reactant, realize the optimization design of catalyst.The composite semiconductor of this method synthesis
Catalyst can realize CO at room temperature2Conversion to HC compounds, there is higher stability.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
The mono- cyanogen ammonia of 3g is weighed, is dissolved with 20mL water, adding the SiO that 3g particle diameters are 10nm2Ball, 10 are stirred at room temperature
Minute, add 0.2g Ce (NO3)3·6H2O, stirring are dissolved it in above solution.Stir 30 minutes at 30 DEG C, afterwards 90
DEG C, dry under stirring condition and remove moisture.It is overnight to be placed in 80 DEG C of baking oven.Obtained powder sample is placed on Muffle furnace
In, 550 DEG C are calcined 3 hours, and brown color product is obtained after cooling.Obtained product is dispersed in 4M NH4In HF solution, remove
Hard template, centrifuge, be dried to obtain final product.
Fig. 1 a and Fig. 1 b are the mesoporous N-CeO of the gained of embodiment 12/mpg-C3N4The scanning electron of composite semiconductor material shows
Micro mirror (SEM) photo.By photo it can be seen that:Prepared mesoporous material has regular hole arrangement architecture.
Fig. 2 a and Fig. 2 b are the mesoporous N-CeO of the gained of embodiment 12/mpg-C3N4The projection electron of composite semiconductor material shows
Micro mirror (TEM) photo and high resolution electron microscopy (HRTEM) photo.As can be seen from the figure the aperture of obtained semi-conducting material is big
Small about 10nm.
Fig. 3 a are the mesoporous N-CeO of the gained of embodiment 12/mpg-C3N4The N of composite semiconductor material2Adsorption/desorption isothermal is bent
Line;Fig. 3 b are the mesoporous N-CeO of the gained of embodiment 12/mpg-C3N4The corresponding graph of pore diameter distribution of composite semiconductor material.Knot
The explainable prepared mesoporous material specific surface areas of conjunction Fig. 3 a and Fig. 3 b are higher, and pore size is about 10nm.
Industrial applicability:Preparation is simple by the present invention, and method is novel, and cost is low, efficiency high, in CO2Light is urged
Change the fields such as conversion and show wide application prospect.