CN105396606B - A kind of cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material and preparation method thereof - Google Patents
A kind of cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material and preparation method thereof Download PDFInfo
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- CN105396606B CN105396606B CN201510841674.9A CN201510841674A CN105396606B CN 105396606 B CN105396606 B CN 105396606B CN 201510841674 A CN201510841674 A CN 201510841674A CN 105396606 B CN105396606 B CN 105396606B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 42
- 239000002096 quantum dot Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 22
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002604 ultrasonography Methods 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical class [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 5
- 150000007974 melamines Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 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 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 2
- 241000165940 Houjia Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- -1 carbon nitrides Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
-
- B01J35/39—
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
Abstract
The invention provides a kind of cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material and preparation method thereof, cerium oxide is embedded in class graphene phase carbon nitride layer structure, nitrogen-doped graphene quantum dot is supported on class graphene phase carbon nitride, so as to form composite photocatalyst material.The present invention has expanded the photoresponse scope of class graphene phase carbon nitride using the doping of nitrogen-doped graphene quantum dot, composite photocatalyst material is had efficient photocatalytic activity using quick photo-generate electron-hole separating effect and electron transfer capabilities between nitrogen-doped graphene quantum dot, cerium oxide, class graphene phase carbon nitride.
Description
Technical field
The present invention relates to a kind of cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material and its
Preparation method, belong to photochemical catalyst preparing technical field.
Background technology
At this stage, people's exploitation and the conductor photocatalysis material developed can only absorb the sun for only accounting for and arriving at the earth mostly
It is relatively low less than 5 % ultraviolet light, solar energy utilization ratio in power spectrum.Therefore, find and synthesizing efficient, stably, low cost it is visible
Catalysis material is the key of decomposing water with solar energy hydrogen manufacturing research.
In recent years, the photocatalytic activity of the composite with inorganic non-metallic structure causes the note of research workers
Meaning.Research finds that inorganic non-metallic structural semiconductor material has special band structure and carrier transport characteristic, is urged in light
The compound of photo-generated carrier can effectively be suppressed by changing in reaction, so as to improve quantum efficiency.
Graphene is a kind of new material for the individual layer laminated structure being made up of carbon atom, and monolayer carbon original thickness not only makes it not
The growth of function nano material is suitable only for, and there is good electronic conductivity, has been acknowledged as the ideal of catalyst
Carrier material；Experiment is controlled silver orthophosphate nucleation and growth during reaction, made using graphene oxide as precursor material
Zinc oxide/silver orthophosphate/graphene the composite photocatalyst material ultimately generated has homogeneous pattern and less size；
It is scattered well that the high transmission rate of graphene, high specific surface area make obtained composite photocatalyst material have in the solution
Property and adsorptivity；Its high electrical conductance further speeds up the separation of Pair production, extends the life-span of active component, enhances
The catalytic activity of composite photocatalyst material.
2009, Wang et al. is again innovative to be applied to photocatalysis field by the carbon nitride material of graphite-like structure,
So that catalysis material is extended to metal-free catalysis material body by traditional catalysis material system containing metal
System.Carbon nitride material has 1) rich content of the raw material in nature and cheap as catalysis material；2)
High heat endurance and chemical stability；3) narrow optical band gap, and the suitable evident characteristic such as conduction band and valence band location,
So that carbon nitride material is more and more paid attention in the research of photocatalysis science.
Graphite-like structure（Lamellar graphite phase）Carbonitride（g-C3N4）It is special with the particular semiconductor optics similar with graphene
Property, it is applied to as visible light-responded catalyst in light-catalyzed reaction, but its photocatalytic activity need further to improve.
The content of the invention
In order to improve graphite-like structure（Lamellar graphite phase）Carbonitride（g-C3N4）Photocatalytic activity, the invention provides
A kind of cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material and preparation method thereof, material of the invention
Expect that simple preparation manipulation, low production cost, the yield of synthesis are higher, purity is high and reproducible, is adapted to extension production
It is required that.
The technical thought of the present invention is to improve the absorbing properties of class graphene phase carbon nitride by graphene quantum dot,
The characteristics of using cerium oxide industry monosodium glutamate, the surface-active of class graphene phase carbon nitride is improved, and mutually nitrogenized in class graphene
Catalytic action is played in carbon preparation process, promotes the generation of class graphene phase carbon nitride, improves yield.A kind of cerium oxide/graphene
Quantum dot/class graphene phase carbon nitride composite photocatalyst material, it is characterized in that：Cerium oxide is embedded in class graphene phase carbon nitride layer
In shape structure, nitrogen-doped graphene quantum dot is supported on class graphene phase carbon nitride, so as to form composite photocatalyst material.
The preparation method of above-mentioned cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material, it is walked
It is rapid as follows：
（1）Weigh 12-13 grams of melamine, 0.2-0.5g cerium oxalates are added in agate mortar and grind uniform, Ran Houjia
Enter in the alumina crucible for being 25 milliliters to capacity, and be put into constant temperature 2 ~ 4 hours in 610 DEG C ~ 660 DEG C of Muffle furnace, obtain light
The class graphene phase carbon nitride for being inlaid with cerium oxide of yellow；
（2）Nitrogen-doped graphene quantum dot synthesizes：0.8 ~ 0.9 gram of citric acid and 0.65 ~ 0.95 gram of urea is taken to be dissolved in
In the deionized water of 15-20 milliliters, fully it is added to after dissolving in 50 milliliters of reactors, is placed in 160 ~ 180 DEG C of forced air drying
Constant temperature 8 ~ 12 hours in case, it is cooled to normal temperature and can obtain finely dispersed nitrogen-doped graphene quantum dot solution；Take 1 ~ 3 milliliter
Nitrogen-doped graphene quantum dot solution is scattered in 30 ml deionized waters, and solution A is obtained after ultrasound；
（3）Take 0.1 ~ 0.5 gram of step（1）Obtained class graphene phase carbon nitride is dissolved in 10 ~ 20 milliliters of water, ultrasound 1 ~ 5
Hour, then solution A is slowly added to, is stirred 15 ~ 20 hours under normal temperature condition, obtains turbid solution B；
（4）Then turbid solution B is filtered, washed and dried, obtains target composite photocatalyst material.
It is an advantage of the invention that：1st, the light of class graphene phase carbon nitride has been expanded in the doping of nitrogen-doped graphene quantum dot
Response range, add absorption under visible light；2 at the same make use of the optical sensibilization of nitrogen-doped graphene quantum dot with
Superpower electronic conduction ability, the compound of light induced electron and hole is not only inhibited, while improve the utilization rate of light, and utilized
The characteristics of cerium oxide electron transfer is easy, quick light induced electron-hole separation between three kinds of materials of photocatalytic process person
Effect and electron transfer capabilities make composite photocatalyst material have efficient photocatalytic activity；3rd, raw material of the invention is inexpensively easy
, synthetic method is simple, and synthetic yield and purity are higher, and experimental repeatability is good, is adapted to the requirement of extension production.
Brief description of the drawings
Fig. 1 is the XRD of the products obtained therefrom of embodiment 1.
Fig. 2 is that the SEM of the products obtained therefrom of embodiment 1 schemes.
Fig. 3 is the UV-vis DRS figure of embodiment 1-5 catalyst.
Fig. 4 is non-impurity-doped class graphene phase carbon nitride and the embodiment 1-5 production of the photocatalysis under the induction of simulated solar irradiation
The design sketch of hydrogen, a- non-impurity-doped class graphene phase carbon nitrides in figure, b- embodiments 1, c- embodiments 2, d- embodiments 3, e- are implemented
Example 4, f- embodiments 5.
Fig. 5 is the composite photocatalyst material of embodiment 3 in the ultraviolet of degradative reduction methylene blue illumination 0,2,4,6,8 hours
It can be seen that all band figure.
Embodiment
Embodiment 1
（1）Weigh 12 grams of melamines, 0.5g cerium oxalates are added to grinding in agate mortar and uniformly, are then added to capacity
For in 25 milliliters of alumina crucibles, and constant temperature 4 hours in 610 DEG C of Muffle furnace are put into, obtain flaxen being inlaid with oxidation
The class graphene phase carbon nitride of cerium；
（2）Nitrogen-doped graphene quantum dot synthesizes：Take 0.8 gram of citric acid and 0.65 gram of urea is dissolved in 15 milliliters and gone
In ionized water, fully it is added to after dissolving in 50 milliliters of reactors, is placed in constant temperature 8 hours in 160 DEG C of air dry oven, cooled down
Finely dispersed nitrogen-doped graphene quantum dot solution is can obtain to normal temperature；Take 2 milliliters of nitrogen-doped graphene quantum dot solutions
It is scattered in 30 ml deionized waters, solution A is obtained after ultrasound；
（3）Take 0.1 gram of step（1）Obtained class graphene phase carbon nitride is dissolved in 10 milliliters of water, ultrasound 1 hour, then
Solution A is slowly added to, is stirred 15 hours under normal temperature condition, obtains turbid solution B；
（4）Then turbid solution B is filtered, washed and dried, obtains target composite photocatalyst material.
Embodiment 2
（1）Weigh 13 grams of melamines, 0.5g cerium oxalates are added to grinding in agate mortar and uniformly, are then added to capacity
For in 25 milliliters of alumina crucibles, and constant temperature 2 hours in 660 DEG C of Muffle furnace are put into, obtain flaxen being inlaid with oxidation
The class graphene phase carbon nitride of cerium；
（2）Nitrogen-doped graphene quantum dot synthesizes：Take 0.9 gram of citric acid and 0.95 gram of urea is dissolved in 20 milliliters and gone
In ionized water, fully it is added to after dissolving in 50 milliliters of reactors, is placed in constant temperature 12 hours in 180 DEG C of air dry oven, it is cold
But it can obtain finely dispersed nitrogen-doped graphene quantum dot solution to normal temperature；Take 3 milliliters of nitrogen-doped graphene quantum dots molten
Liquid is scattered in 30 ml deionized waters, and solution A is obtained after ultrasound；
（3）Take 0.5 gram of step（1）Obtained class graphene phase carbon nitride is dissolved in 20 milliliters of water, ultrasound 5 hours, then
Solution A is slowly added to, is stirred 20 hours under normal temperature condition, obtains turbid solution B；
（4）Then turbid solution B is filtered, washed and dried, obtains target composite photocatalyst material.
Embodiment 3
（1）Weigh 12 grams of melamines, 0.3g cerium oxalates are added to grinding in agate mortar and uniformly, are then added to capacity
For in 25 milliliters of alumina crucibles, and constant temperature 3 hours in 650 DEG C of Muffle furnace are put into, obtain flaxen being inlaid with oxidation
The class graphene phase carbon nitride of cerium；
（2）Nitrogen-doped graphene quantum dot synthesizes：Take 0.8 gram of citric acid and 0.7 gram of urea is dissolved in 20 milliliters and gone
In ionized water, fully it is added to after dissolving in 50 milliliters of reactors, is placed in constant temperature 10 hours in 170 DEG C of air dry oven, it is cold
But it can obtain finely dispersed nitrogen-doped graphene quantum dot solution to normal temperature；Take 2 milliliters of nitrogen-doped graphene quantum dots molten
Liquid is scattered in 30 ml deionized waters, and solution A is obtained after ultrasound；
（3）Take 0.2 gram of step（1）Obtained class graphene phase carbon nitride is dissolved in 10 milliliters of water, ultrasound 3 hours, then
Solution A is slowly added to, is stirred 15 hours under normal temperature condition, obtains turbid solution B；
（4）Then turbid solution B is filtered, washed and dried, obtains target composite photocatalyst material.
Embodiment 4
（1）Weigh 12 grams of melamines, 0.3g cerium oxalates are added to grinding in agate mortar and uniformly, are then added to capacity
For in 25 milliliters of alumina crucibles, and constant temperature 3 hours in 650 DEG C of Muffle furnace are put into, obtain flaxen being inlaid with oxidation
The class graphene phase carbon nitride of cerium；
（2）Nitrogen-doped graphene quantum dot synthesizes：Take 0.8 gram of citric acid and 0.7 gram of urea is dissolved in 20 milliliters and gone
In ionized water, fully it is added to after dissolving in 50 milliliters of reactors, is placed in constant temperature 10 hours in 170 DEG C of air dry oven, it is cold
But it can obtain finely dispersed nitrogen-doped graphene quantum dot solution to normal temperature；Take 2 milliliters of nitrogen-doped graphene quantum dots molten
Liquid is scattered in 30 ml deionized waters, and solution A is obtained after ultrasound；
（3）Take 0.3 gram of step（1）Obtained class graphene phase carbon nitride is dissolved in 10 milliliters of water, ultrasound 3 hours, then
Solution A is slowly added to, is stirred 15 hours under normal temperature condition, obtains turbid solution B；
（4）Then turbid solution B is filtered, washed and dried, obtains target composite photocatalyst material.
Embodiment 5
（1）Weigh 12 grams of melamines, 0.3g cerium oxalates are added to grinding in agate mortar and uniformly, are then added to capacity
For in 25 milliliters of alumina crucibles, and constant temperature 3 hours in 650 DEG C of Muffle furnace are put into, obtain flaxen being inlaid with oxidation
The class graphene phase carbon nitride of cerium；
（2）Nitrogen-doped graphene quantum dot synthesizes：Take 0.8 gram of citric acid and 0.7 gram of urea is dissolved in 20 milliliters and gone
In ionized water, fully it is added to after dissolving in 50 milliliters of reactors, is placed in constant temperature 10 hours in 170 DEG C of air dry oven, it is cold
But it can obtain finely dispersed nitrogen-doped graphene quantum dot solution to normal temperature；Take 2 milliliters of nitrogen-doped graphene quantum dots molten
Liquid is scattered in 30 ml deionized waters, and solution A is obtained after ultrasound；
（3）Take 0.4 gram of step（1）Obtained class graphene phase carbon nitride is dissolved in 10 milliliters of water, ultrasound 3 hours, then
Solution A is slowly added to, is stirred 15 hours under normal temperature condition, obtains turbid solution B；
（4）Then turbid solution B is filtered, washed and dried, obtains target composite photocatalyst material.
Make XRD analysis to embodiment 1-5 products therefroms, the XRD of embodiment 1 is as shown in figure 1, the XRD of other embodiment
Scheme similar, showing cerium oxide is filled into class graphene phase carbon nitride, and is the structure for changing class graphene phase carbon nitride.
What Fig. 2 was provided is the SEM of the product of embodiment 3（SEM）Photo, product is main as seen from the figure
It is that there is loose porous class graphene phase carbon nitride layer structure, cerium oxide is embedded in class graphene phase carbon nitride layer structure
In.The graphene quantum dot load class graphene phase carbon nitride of prepared different proportion is found out from Fig. 3 Raman spectrum
Raman peaks are completely the same, illustrate that cerium oxide has successfully been doped into class graphene phase carbon nitride lattice.
Tested from Fig. 4, under a closed glass photoreaction system simulated solar irradiation, cerium oxide of the invention/
Graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material has good production hydrogen effect under simulated solar irradiation,
Effective combination by photochemical catalytic oxidation and photo catalytic reduction technology is realized, substantially increases the utilization rate of sunshine.
As shown in Figure 5, cerium oxide/graphene quantum dot of embodiment 3/class graphene phase carbon nitride composite photocatalyst material
The yield that methylene blue is converted into methanol and ethanol respectively reaches 9.67 and 4.34 moles per grams/hour, the removal of methylene blue
Rate is up to 99.99%.
Claims (2)
1. a kind of cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material, it is characterized in that：Cerium oxide
It is embedded in class graphene phase carbon nitride layer structure, nitrogen-doped graphene quantum dot is supported on class graphene phase carbon nitride,
So as to form composite photocatalyst material.
2. a kind of preparation method of cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material, its feature
It is that step is as follows：
（1）Weigh 12-13 grams of melamine, 0.2-0.5g cerium oxalates are added to grinding in agate mortar and uniformly, are then added to
Capacity is in 25 milliliters of alumina crucible, and is put into constant temperature 2 ~ 4 hours in 610 DEG C ~ 660 DEG C of Muffle furnace, obtains faint yellow
The class graphene phase carbon nitride for being inlaid with cerium oxide；
（2）Nitrogen-doped graphene quantum dot synthesizes：0.8 ~ 0.9 gram of citric acid and 0.65 ~ 0.95 gram of urea is taken to be dissolved in 15-20
In the deionized water of milliliter, fully it is added in 50 milliliters of reactors, is placed in 160 ~ 180 DEG C of air dry oven permanent after dissolving
Temperature 8 ~ 12 hours, is cooled to normal temperature and can obtain finely dispersed nitrogen-doped graphene quantum dot solution；Take 1 ~ 3 milliliter of N doping
Graphene quantum dot solution is scattered in 30 ml deionized waters, and solution A is obtained after ultrasound；
（3）Take 0.1 ~ 0.5 gram of step（1）Obtained class graphene phase carbon nitride is dissolved in 10 ~ 20 milliliters of water, ultrasound 1 ~ 5 hour,
Then solution A is slowly added to, is stirred 15 ~ 20 hours under normal temperature condition, obtain turbid solution B；
（4）Then turbid solution B is filtered, washed and dried, obtains target composite photocatalyst material.
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| CN201510841674.9A CN105396606B (en) | 2015-11-28 | 2015-11-28 | A kind of cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material and preparation method thereof |
| CN201710715282.7A CN107376976A (en) | 2015-11-28 | 2015-11-28 | A kind of preparation method of cerium oxide/graphene quantum dot/class graphene phase carbon nitride composite photocatalyst material |
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| CN106311307B (en) * | 2016-08-22 | 2019-05-31 | 江苏大学 | A method of preparing heterojunction photocatalyst |
| CN106345507B (en) * | 2016-08-22 | 2019-02-19 | 江苏大学 | A kind of preparation method of composite photo-catalyst |
| CN106540732B (en) * | 2016-10-20 | 2019-03-22 | 中国石油大学(北京) | A kind of redox graphene/mesoporous graphitization carbon nitride material and preparation method |
| CN106586954B (en) * | 2016-12-28 | 2018-09-25 | 安徽工业大学 | Use RhNiFe/CeO2@P@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation |
| CN106672899B (en) * | 2016-12-28 | 2018-09-25 | 安徽工业大学 | Use RhNiFe/CeO2@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation |
| CN107162048B (en) * | 2017-07-10 | 2019-01-25 | 闽南师范大学 | A kind of preparation method of titanium dioxide/nitridation carbon composite nano-material |
| CN107983386B (en) * | 2017-12-01 | 2020-12-08 | 江苏理工学院 | Ultrathin BiOCl/nitrogen-doped graphene quantum dot composite photocatalyst and preparation method thereof |
| CN108325550A (en) * | 2018-01-22 | 2018-07-27 | 江苏理工学院 | A kind of Preparation method and use of nitrogen-doped graphene quantum dot/zinc oxide/carbonitride composite visible light catalyst |
| CN110954580B (en) * | 2019-01-31 | 2021-10-15 | 河海大学 | Preparation method and application method of membrane electrode |
| CN110252372A (en) * | 2019-05-31 | 2019-09-20 | 江苏大学 | A kind of two dimension rGO/R-CeO2The preparation method of/CNNS hierarchical structure composite photo-catalyst |
| CN110835104A (en) * | 2019-10-28 | 2020-02-25 | 深圳先进技术研究院 | Preparation method of nitrogen-doped carbon nanosheet, negative electrode active material and dual-ion battery |
| CN110828186B (en) * | 2019-11-18 | 2021-09-28 | 黑龙江科技大学 | CeO (CeO)2Preparation method of modified nitrogen-doped graphene DSSC counter electrode |
| CN111704155B (en) * | 2020-01-20 | 2021-04-27 | 中国石油大学(华东) | CeO (CeO)2/g-C3N4Humidity sensor of hybrid membrane and preparation method and application thereof |
| CN114225956A (en) * | 2021-12-29 | 2022-03-25 | 南京大学环境规划设计研究院集团股份公司 | Preparation method and application of composite photocatalytic material for degrading antibiotics and hexavalent chromium |
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| CN104150473A (en) * | 2014-08-04 | 2014-11-19 | 江苏大学 | Chemical preparation method for nitrogen-doped graphene quantum dot |
| CN104399510B (en) * | 2014-12-08 | 2016-08-03 | 中国科学院化学研究所 | A kind of preparation method of the optic catalytic composite material of graphite oxide and carbonitride |
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