CN106475127A - A kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst and preparation method thereof - Google Patents
A kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 138
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- 239000002096 quantum dot Substances 0.000 title claims abstract description 78
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 36
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004005 microsphere Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 8
- 229960004756 ethanol Drugs 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- -1 graphite Alkene Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 16
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- 230000009881 electrostatic interaction Effects 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012779 reinforcing material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
-
- B01J35/39—
-
- B01J35/51—
Abstract
The present invention provides a kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst and preparation method thereof.This nitrogen-doped graphene quantum dot is distributed in volumetric surface and the inside of titanium dioxide solid microsphere, and nitrogen-doped graphene quantum dot/mesoporous TiO 2 is spherical, and its diameter, in 400 600nm, has meso-hole structure, and titanium dioxide is pure anatase titanium dioxide.Preparation method is the graphene quantum dot of synthetic nitrogen doping first, then adopts sol-gal process fabricated in situ graphene quantum dot/mesoporous TiO 2.Graphene quantum dot and structure directing agent, due to electrostatic interaction, are progressively distributed to titanium dioxide microballoon sphere volumetric surface and inside in titanium source hydrolytic process with structure directing agent.Graphene quantum dot, as the electron acceptor of titanium dioxide and carrier, increases the disengaging time of electron hole, reaches the purpose of reinforcing material photocatalysis performance.The present invention relates to method, simple to operate, synthesis cycle is short, easy to control, and the hydrogen-producing speed of material is up to 0.5mmol h‑1.
Description
Technical field
The present invention relates to the energy and environmental area are and in particular to a kind of nitrogen-doped graphene quantum dot/mesoporous TiO 2
Photocatalyst and preparation method thereof.
Background technology
Titanium dioxide is a kind of important semiconductor light-catalyst, is widely used in degradation of organic dyes, photocatalytic cleavage
Water.When increasing the specific surface area of titanium dioxide, because big specific surface area increased titania molecule and adsorbent
Effectively chemical contact area, thus there being more binding molecule to act on titanium dioxide under the irradiation of light, therefore enhances light
Catalytic performance.The P25 type commercial titanium dioxide powder that this approach is mainly produced with Degussa company is most widely used, its ratio
Surface area is 50 (± 15) m2/g；Two is by preparing mesoporous titanium dioxide material, due to the internal mesoporous presence of granule, dioxy
The specific surface area changing titanium increases, and its photocatalysis performance is also greatly improved.For example, Sanchez et al. passes through collosol and gel
Method prepares mesoporous titanium dioxide film, illustrates excellent thermal stability and photocatalysis performance；Researchers' contrast afterwards
The titanium dioxide of ball and hollow structure in medicine ball, ball, experiment finds, increases ball and hollow structure pole in the ball of specific surface area
Its photocatalysis performance of big increase；Caruso etc. utilizes the Detitanium-ore-type mesoporous TiO 2 of soft template method synthesis various sizes little
Ball, its specific surface area reaches 422m2/ g, exceeds more than 8 times than P25.
However, when titanium dioxide is subject to ultraviolet excitation, the light induced electron of generation is easily compound with hole, thus reducing
Photocatalysis performance.Therefore, how to stop light induced electron with hole-recombination thus improving photocatalysis performance is this area research
Personnel are urgently to be resolved hurrily.
Content of the invention
Easily compound for titanium dioxide photoproduction electron hole, the invention provides a kind of enhanced nitrogen of photocatalysis performance is mixed
Miscellaneous graphene quantum dot/mesopore titania photocatalyst and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is：
A kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst, described nitrogen-doped graphene quantum dot divides
In the volumetric surface of titanium dioxide solid microsphere and inside, nitrogen-doped graphene quantum dot/mesoporous TiO 2 is spherical to cloth, its
Diameter, in 400-600nm, has meso-hole structure, and titanium dioxide is pure anatase titanium dioxide.
A kind of preparation method of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst is it is characterised in that it wraps
Include following steps：
1) citric acid and nitrogen source are added in appropriate amount of deionized water and obtain neutral mixed solution, described mixed solution is surpassed
React 4 hours at being transferred to 140-180 DEG C in hydrothermal reaction kettle after sound dispersion；Washed product is dried and be can get N doping graphite
Alkene quantum dot, described nitrogen source is thiourea or carbamide, and the mol ratio of described citric acid and nitrogen source is 1:3；
2) cetylamine is dissolved in ethanol solution and stirs；Then taking step 1) the nitrogen-doped graphene quantum dot of gained is molten
In deionized water, ultrasonic and add to above-mentioned solution, after stirring, add Klorvess Liquid and isopropyl titanate, so
After stand, reaction solution filters and uses dehydrated alcohol cyclic washing, is dried before obtaining nitrogen-doped graphene quantum dot/titanium dioxide
Body, described graphene quantum dot is less than 11.3g/L with the mass volume ratio of isopropyl titanate (purity 95%)；
3) take step 2) in dried product be dissolved in dehydrated alcohol and the mixed solution of deionized water, anti-at 160 DEG C
Answer 16 hours；
4) after step 3) after product is cooled to room temperature, filtering solution simultaneously repeatedly washs, and is then dried and obtains N doping
Graphene quantum dot/mesoporous TiO 2 microsphere；
5) by step 4) in nitrogen-doped graphene quantum dot/mesoporous TiO 2 microsphere roasting obtains in an inert atmosphere
Nitrogen-doped graphene quantum dot/mesopore titania photocatalyst.
In such scheme, step 3) in, ethanol：The volume ratio of deionized water is 2:1.
In such scheme, step 5) in, sintering temperature is 400 DEG C -500 DEG C, and roasting time is 2-3 hour.
In such scheme, step 2) in, Klorvess Liquid concentration is 0.1mol/L.
The present invention synthesizes the graphene quantum dot of N doping first, then adopts sol-gel process fabricated in situ Graphene
Quantum dot/mesoporous TiO 2.Graphene quantum dot and structure directing agent due to electrostatic interaction, in titanium source hydrolytic process
Progressively it is distributed to titanium dioxide microballoon sphere volumetric surface and inside with structure directing agent.
The present invention has the beneficial effect that：
1) with nitrogen-doped graphene quantum dot, isopropyl titanate is presoma to the present invention, and cetylamine is structure directing agent, leads to
Cross sol-gel process one step fabricated in situ nitrogen-doped graphene quantum dot/mesopore titania photocatalyst, its photocatalysis performance
It is significantly improved.
2) present invention solves the soda acid pollution producing in graphene quantum dot preparation process, with citric acid, thiourea/carbamide
For raw material, prepare graphene quantum dot, its reactant liquor is neutral reaction liquid.
3) this significantly alleviates the easily compound phenomenon of photo-generate electron-hole of titanium dioxide optical catalyst generation, graphite
Alkene quantum dot penetrates into inside bead with the gathering of titania nanoparticles, and quantum dot is attached to titanium dioxide microballoon sphere table
On face and internal grain, high-resolution transmission photo is it can also be seen that in photocatalytic process from behind, graphene quantum dot and two
Titanium oxide grain is closely located to, and this allows in photocatalytic process, and graphene quantum dot can shift rapidly titanium dioxide generation
Light induced electron, improves photocatalysis efficiency because of its high conductivity.
Brief description
Fig. 1 is the SEM figure of the nitrogen-doped graphene quantum dot/titanium dioxide microballoon sphere of gained in embodiment 1.
Fig. 2 is the nitrogen-doped graphene quantum dot/mesoporous TiO 2 semiconductor light-catalyst prepared by embodiment 1
SEM schemes.
Fig. 3 be prepared nitrogen-doped graphene quantum dot/TiO 2 precursor microsphere (GQDs-PB) in embodiment 1,
Nitrogen-doped graphene quantum dot after hydro-thermal/titanium dioxide (GQDs-PB-HT) and nitrogen-doped graphene quantum dot/mesoporous two
The XRD spectrum of titania photocatalyst (GQDs/PB-HT-Ar).
Fig. 4 is the SEM figure of prepared mesopore titania photocatalyst in comparative example 1.
Fig. 5 is mesopore titania photocatalyst and nitrogen-doped graphene quantum dot/mesopore titania photocatalyst exists
Under the conditions of ultraviolet-visible, the activity figure of catalytic decomposition Aquatic product hydrogen.
Fig. 6 is that the high-resolution transmission of prepared nitrogen-doped graphene quantum dot/titanium dioxide microballoon sphere in embodiment 1 is micro-
Photo.
Specific embodiment
For a better understanding of the present invention, it is further elucidated with present disclosure with reference to embodiment, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
The present embodiment provides a kind of preparation method of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst, tool
Body step is as follows：
1) 0.23g citric acid and 0.23g thiourea (or 0.18g carbamide) are added in appropriate amount of deionized water, will be described
It is transferred to after mixed solution ultrasonic disperse in hydrothermal reaction kettle, react 4 hours at 160 DEG C；Washed product is dried and be can get nitrogen
Doped graphene quantum dot.
2) 2.648g cetylamine is dissolved in 400ml ethanol solution and stirs.Then taking step 1) nitrogen of gained mixes
Miscellaneous graphene quantum dot 48mg is dissolved in 1.60ml deionized water, ultrasonic and add to above-mentioned solution, after stirring, adds
1.60ml Klorvess Liquid (0.1mol/L) and 8.8ml isopropyl titanate (purity is 95%), then stand 18 hours.Reaction is molten
Liquid filters and uses dehydrated alcohol cyclic washing, is dried and obtains nitrogen-doped graphene quantum dot/titanium dioxide precursor；
3) take step 2) in dried product be dissolved in 30ml dehydrated alcohol and the mixed solution of 15ml deionized water,
React 16 hours at 160 DEG C；
4) after step 3) after product is cooled to room temperature, filtering solution is simultaneously repeatedly washed with ethanol solution, is then dried
Obtain nitrogen-doped graphene quantum dot/mesoporous TiO 2 microsphere；
5) by step 4) in nitrogen-doped graphene quantum dot/mesoporous TiO 2 microsphere roast in 500 DEG C of inert atmospheres
Burn 2-3 hour and obtain nitrogen-doped graphene quantum dot/mesopore titania photocatalyst.
Interpretation of result
Fig. 1 is the SEM figure of the nitrogen-doped graphene quantum dot/titanium dioxide precursor of gained in embodiment 1, can from figure
To find out that bead is in single dispersing, sphere is smooth, and sphere diameter is in 500nm.
Can be clearly seen that microsphere surface is piled up by nano-particle from Fig. 2 to form, and have mesopore orbit, channel diameter
In 20nm about, after hydro-thermal is described, amorphous titania is to crystalline transformation.
In Fig. 3 XRD spectrum, it is evident that nitrogen-doped graphene quantum dot/TiO 2 precursor microsphere is no fixed
Kenel, after hydro-thermal, spectral line significantly sharp peak type occurs, provable microsphere has been changed into crystalline state by unformed shape.Calcine it
Sample afterwards becomes apparent from than the crystal formation before calcining, and diffraction maximum has certain widthization phenomenon, illustrates sample on nano-scale
Crystallinity is preferable.And all diffraction maximums of in figure all can belong to Detitanium-ore-type TiO2Crystalline phase.
From the HRTEM picture of Fig. 6, we are clear that titanium dioxide (101) lattice fringe, and titanium dioxide is brilliant
Grain is in close contact with nitrogen-doped graphene quantum dot, and the presence having nitrogen-doped graphene quantum dot in titanium dioxide microballoon sphere is described,
Because position is close between quantum dot and titania, can effectively strengthen the transmission effect of light induced electron in photocatalytic process
Rate, improves photocatalysis performance, and its photocatalysis performance is as shown in Figure 5.
Embodiment 2
The present embodiment is similar to Example 1, difference be nitrogen-doped graphene quantum point mass in embodiment 1 is
96mg, can see that in titanium dioxide preparation process upper solution color is blueness, represents in solution and be dispersed with N doping stone
Black alkene quantum dot, and embodiment 1 at the middle and upper levels solution be colourless.Find after test, prepared nitrogen-doped graphene quantum dot/
The morphology of mesopore titania photocatalyst is same as Example 1, and its photocatalysis performance is as shown in Figure 5.
Embodiment 3
The present embodiment is similar to Example 1, difference be nitrogen-doped graphene quantum point mass in embodiment 1 is
24mg, finds after test, the microstructure shape of prepared nitrogen-doped graphene quantum dot/mesopore titania photocatalyst
Looks are same as Example 1, and its photocatalysis performance is as shown in Figure 5.
Comparative example 1
1) take 2.648g cetylamine to be dissolved in dehydrated alcohol in 400ml, ultrasonic agitation, after cetylamine is completely dissolved, add
1.60ml deionized water and 1.60ml KCl solution (0.1mol/L).It is subsequently adding 8.8ml isopropyl titanate, stand 18 hours；
2) by step 1) standing after solution sucking filtration and washing is repeated several times with absolute ethanol washing, gained sample is put in 60
Dry in DEG C baking oven, gained sample is TiO 2 precursor microsphere；
3) taking step 2) gained sample is dissolved in 30ml dehydrated alcohol and the mixed solution of 15ml deionized water, ultrasonic agitation
Afterwards, it is transferred in 50ml hydrothermal reaction kettle, 160 DEG C are reacted 16 hours.After reaction completes to be cooled to room temperature, by reactant liquor sucking filtration simultaneously
Repeatedly washed with ethanol solution, then the sample after washing is dried, obtain mesoporous TiO 2；
4) by step 3) in mesoporous TiO 2 calcine 2-3 hour in 500 DEG C of inert atmospheres and obtain meso-porous titanium dioxide
Titanium photocatalyst (PB-HT-Ar).
Fig. 4 is the SEM figure of the mesopore titania photocatalyst prepared by comparative example 1, it is evident that its microstructure
Compared with graphene quantum dot/mesopore titania photocatalyst prepared by with embodiment 1 for the pattern, do not send out into change, say
Bright nitrogen-doped graphene quantum dot will not produce impact to mesoporous TiO 2 morphology.
Comparative example 2
1) take 2.648g cetylamine to be dissolved in dehydrated alcohol in 400ml, ultrasonic agitation, after cetylamine is completely dissolved, add
1.60ml deionized water and 1.60ml KCl solution (0.1mol/L).It is subsequently adding 8.8ml isopropyl titanate, stand 18 hours；
2) by step 1) standing after solution sucking filtration and washing is repeated several times with absolute ethanol washing, gained sample is put in 60
Dry in DEG C baking oven, gained sample is TiO 2 precursor microsphere；
3) taking step 2) gained sample is dissolved in 30ml dehydrated alcohol and the mixed solution of 15ml deionized water, ultrasonic agitation
Afterwards, add appropriate graphene oxide solution (graphene oxide quality is 48mg), after mix homogeneously, be transferred to 50ml hydro-thermal reaction
In kettle, 160 DEG C are reacted 16 hours.After reaction completes to be cooled to room temperature, repeatedly wash by reactant liquor sucking filtration and with ethanol solution, then
Sample after washing is dried, obtains the mesoporous TiO 2 of graphene coated；
4) by step 3) in sample calcine 2-3 hour in 500 DEG C of inert atmospheres and obtain mesoporous titanium dioxide photocatalytic
Agent (PB-GO-Ar).
In order to study nitrogen-doped graphene quantum dot/mesoporous TiO 2 semiconductor light-catalyst prepared by the present invention
Photocatalysis performance, itself and the mesopore titania photocatalyst prepared by comparative example 1 are carried out the experiment of photodissociation Aquatic product hydrogen respectively.Tool
Body step is as follows：By the nitrogen-doped graphene quantum dot/mesoporous TiO 2 prepared by embodiment 1-3 and comparative example 1 and right
Prepared mesoporous TiO 2 20mg in ratio 2 is added separately in 40ml methanol and the mixed solution of 40ml deionized water,
It is added in an airtight glass reactor after instilling 51 μ l chloroplatinic acid (10mM) ultrasonic disperse again and stirs, be placed in 300W xenon
Under lamp (PLS-SXE300C, Bo Fei Lay Science and Technology Ltd.).The gas producing passes through Agilent 7890B chromatographic,
When turning on light, setting source current is 19A, often crosses and takes within 1 hour a point, takes 5 points altogether.
Fig. 5 is mesopore titania photocatalyst, different addition quantity nitrogen-doped graphene quantum dot/mesoporous TiO 2 in purple
Under outer visible light conditions, the activity figure of catalytic decomposition Aquatic product hydrogen, when undoped p graphene quantum dot, titanium dioxide optical catalyst
Hydrogen yield be up to 0.13mmol/h, so low hydrogen generation efficiency be because titanium dioxide produce light induced electron and hole
Easily compound, thus limiting its photocatalysis performance, and stable circulation is also very poor.And mixing nitrogen-doped graphene quantum dot
Afterwards, the hydrogen rate of high yield of embodiment 1, embodiment 2 and embodiment 3 is respectively 0.51mmol/h, 0.54mmol/h, 0.30mmol/
H, this is mainly attributed to the high electron mobility of GQDs so that graphene quantum dot becomes electron transit mediator, extends electronics
With the disengaging time in hole, thus greatly improving the photocatalysis performance of this catalyst.And in comparative example 1, pure titinium dioxide
Produce hydrogen rate and be only 0.196mmol/h, the product hydrogen rate of the graphene coated titanium dioxide in comparative example 2 is only 0.227mmol/h.All
High not as mixing the hydrogen generation efficiency after quantum dot.So graphene quantum dot/mesoporous TiO 2 the light prepared by the present invention is urged
Agent is more more superior than the photocatalysis performance of mesoporous TiO 2.
Claims (5)
1. a kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst is it is characterised in that described nitrogen-doped graphene
Quantum dot is distributed in volumetric surface and the inside of titanium dioxide solid microsphere, nitrogen-doped graphene quantum dot/mesoporous TiO 2
For spherical, its diameter, in 400-600nm, has meso-hole structure, and titanium dioxide is pure anatase titanium dioxide.
2. a kind of preparation method of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst is it is characterised in that it includes
Following steps：
1) citric acid and nitrogen source are added in appropriate amount of deionized water and obtain neutral mixed solution, by ultrasonic for described mixed solution point
React 4 hours at being transferred to 140-180 DEG C in hydrothermal reaction kettle after dissipating；Washed product is dried and be can get nitrogen-doped graphene amount
Sub-, described nitrogen source is thiourea or carbamide, and the mol ratio of described citric acid and nitrogen source is 1:3；
2) cetylamine is dissolved in ethanol solution and stirs；Then taking step 1) the nitrogen-doped graphene quantum dot of gained is dissolved in
In ionized water, ultrasonic and add to above-mentioned solution, after stirring, add Klorvess Liquid and isopropyl titanate, Ran Houjing
Put, reaction solution filters and use dehydrated alcohol cyclic washing, be dried and obtain body before nitrogen-doped graphene quantum dot/titanium dioxide
Body, described graphene quantum dot is less than 11.3g/L with isopropyl titanate mass volume ratio；
3) take step 2) in dried product be dissolved in dehydrated alcohol and the mixed solution of deionized water, at 160 DEG C react 16
Hour；
4) after step 3) after product is cooled to room temperature, filtering solution simultaneously repeatedly washs, and is then dried and obtains N doping graphite
Alkene quantum dot/mesoporous TiO 2 microsphere；
5) by step 4) in nitrogen-doped graphene quantum dot/mesoporous TiO 2 microsphere roasting obtains nitrogen and mixes in an inert atmosphere
Miscellaneous graphene quantum dot/mesopore titania photocatalyst.
3. the preparation method of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst according to claim 2, its
It is characterised by, step 3) in, ethanol：The volume ratio of deionized water is 2:1.
4. the preparation method of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst according to claim 2, its
It is characterised by, step 5) in, sintering temperature is 400 DEG C -500 DEG C, and roasting time is 2-3 hour.
5. the preparation method of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst according to claim 2, its
It is characterised by, step 2) in, Klorvess Liquid concentration is 0.1mol/L.
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| CN108164458A (en) * | 2018-02-08 | 2018-06-15 | 浙江师范大学 | A kind of synthetic method of citrazinic acid |
| CN108889329A (en) * | 2018-08-02 | 2018-11-27 | 华东理工大学 | A kind of quantum-dot modified multi-stage porous TiO2-SiO2 photochemical catalyst of carbonitride |
| CN110016731A (en) * | 2019-04-30 | 2019-07-16 | 张慧 | A kind of quantum titanium fibrous material |
| CN110124725A (en) * | 2019-06-25 | 2019-08-16 | 西北师范大学 | A kind of preparation and application hydrogenating titanium dioxide/graphene quantum dot composite material |
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| CN114958147A (en) * | 2021-11-12 | 2022-08-30 | 中国科学院海洋研究所 | Nano hybrid material coating material and synthetic method and application thereof |
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| CN108164458A (en) * | 2018-02-08 | 2018-06-15 | 浙江师范大学 | A kind of synthetic method of citrazinic acid |
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| CN110016731A (en) * | 2019-04-30 | 2019-07-16 | 张慧 | A kind of quantum titanium fibrous material |
| CN110124725A (en) * | 2019-06-25 | 2019-08-16 | 西北师范大学 | A kind of preparation and application hydrogenating titanium dioxide/graphene quantum dot composite material |
| CN110927238A (en) * | 2019-12-12 | 2020-03-27 | 山东理工大学 | Preparation method and application of sandwich type photoelectrochemical sensor for detecting prostate specific antigen |
| CN110927238B (en) * | 2019-12-12 | 2022-10-11 | 山东理工大学 | Preparation method and application of sandwich type photoelectrochemical sensor for detecting prostate specific antigen |
| CN111682222A (en) * | 2020-06-17 | 2020-09-18 | 宁波大学 | Preparation method and catalytic application of Pt-CdS-nitrogen doped graphene quantum dot composite material |
| CN114958147A (en) * | 2021-11-12 | 2022-08-30 | 中国科学院海洋研究所 | Nano hybrid material coating material and synthetic method and application thereof |
| CN114958147B (en) * | 2021-11-12 | 2024-02-06 | 中国科学院海洋研究所 | Nano hybrid material coating material and synthetic method and application thereof |
| CN115739200A (en) * | 2022-11-16 | 2023-03-07 | 吕梁学院 | Preparation method of composite catalyst for efficiently utilizing visible light and near infrared light |
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