CN107376967A - A kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst - Google Patents
A kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 60
- 239000010439 graphite Substances 0.000 title claims abstract description 60
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005917 acylation reaction Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000002608 ionic liquid Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 5
- 239000004471 Glycine Substances 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 5
- 239000008103 glucose Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000000875 high-speed ball milling Methods 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- -1 1,3- dibutyl imidazoles chloros salt Chemical class 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000007306 functionalization reaction Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- 229910005987 Ge3N4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention belongs to optic catalytic composite material technical field, more particularly to a kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst：Using glucose and glycine as carbon matrix precursor and nitrogen presoma, nitrogenous carbon quantum dot is synthesized using high speed ball-milling method；Graphite phase carbon nitride is made using hydro-thermal method；Using hydrophilic ionic-liquid as solvent, nitrogenous carbon quantum dot and graphite phase carbon nitride are combined by acylation reaction, prepare nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst, nitrogenous carbon quantum dot passes through Covalent bonding together with graphite phase carbon nitride.
Description
Technical field
The invention belongs to optic catalytic composite material technical field, more particularly to a kind of nitrogenous carbon quantum dot/graphite-phase nitridation
The preparation method of carbon composite photocatalyst.
Background technology
Photocatalytic hydrogen production by water decomposition is converted into cleaning and highdensity hydrogen using water as raw material, by inexhaustible solar energy
Can, the energy demand of the mankind can be met, but it is free from environmental pollution, have become the optimal side for solving energy shortage and environmental pollution
One of method, there are good potentiality in new energy development field.Photolysis water hydrogen reaction actually light, which excites down, betides half
Hydrogen is made in one catalytic reduction reaction on conductor catalyst surface, light induced electron reductive water.
The ratio of visible ray is about 43% in sunshine, therefore the key for establishing photocatalytic hydrogen production by water decomposition system is exploitation
High activity, environmental protection low price, the photochemical catalyst that can effectively absorb visible ray and be easily recycled.The photochemical catalyst reported now is main
There is metal oxygen (sulphur) compound semiconductor (such as TiO2, ZnO, ZnS, CdS etc.), nano nitride (such as Ta3N5、g-C3N4、β-Ge3N4
Deng), polynary stratiform sulphur compound (such as Cd0.6Zn0.4S、ZnIn2S4、Zn0.8Cd0.2S etc.), nm phosphide (such as GaP nano wires),
Metal composite, polymer (such as polyimides) and nano-sized carbon (such as CNT, graphite oxide, graphene).Wherein, receive
Raw material is cheap, synthesize simple and environmentally-friendly, good light stability, be easy to functionalization and visible light-responded ability is strong because having for rice carbon material
The advantages that and enjoy favor.
Carbon quantum dot with semiconductor property with uniqueness band structure, adjustable band gap, more energy subbands,
Strong visible light-responded ability, controllable particle diameter and it is environmentally friendly the advantages that, electronics transfer phenomena can be produced under excited by visible light, but
The speed of pure carbon quantum dot photodissociation aquatic products hydrogen is less than 50 μm of ol h-1, than relatively low.
The content of the invention
It is an object of the invention to provide a kind of composite catalyst with good photocatalytic hydrogen production by water decomposition efficiency, in order to
Above-mentioned purpose is realized, the present invention has constructed nitrogenous carbon quantum dot/graphite phase carbon nitride with Covalent bonding together by acylation reaction
Composite photo-catalyst,
First using glucose and glycine as carbon matrix precursor and nitrogen presoma, nitrogenous carbon quantum is synthesized using high speed ball-milling method
Point；Graphite phase carbon nitride is made using hydro-thermal method again；Then by acylation reaction by nitrogenous carbon quantum dot and graphite phase carbon nitride
It is combined, prepares nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst, thus nitrogenous carbon quantum dot and graphite-phase nitrogen
Change carbon by Covalent bonding together,
In nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst, the weight/mass percentage composition of nitrogenous carbon quantum dot is
5wt.%~50wt.%,
In the preparation process of nitrogenous carbon quantum dot, the mechanical ball mill time is 0.5~8h, and rotating speed is 580~1000rpm,
Ratio of grinding media to material is 20:1~60:1, a diameter of 5~20mm of agate ball used,
Hydro-thermal method prepare graphite phase carbon nitride during, hydrothermal temperature be 80~220 DEG C, the reaction time be 2~
20h,
When nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst is prepared using acylation reaction, backflow behaviour is first passed through
Work makes nitrogenous carbon quantum dot surface take acid chloride groups, then graphite phase carbon nitride surface is taken hydroxyl, finally by acylated anti-
Nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst should be made,
Return time is 4~24h.
Advantage of the invention is that：Using the ionic liquid with distinct chemical and physical property in acylation reaction as molten
Agent and catalyst, the shortcomings of extraction separation brought during as catalyst is difficult is overcome using the concentrated sulfuric acid；
Nitrogenous carbon quantum dot is dispersed in the surface of graphite phase carbon nitride by way of Covalent bonding together, using containing
The nanometer size effect of nitrogen carbon quantum dot improves the Photocatalyzed Hydrogen Production efficiency of graphite phase carbon nitride, and synthetic method is simple, and light is urged
It is good to change effect.
Brief description of the drawings
Fig. 1 is the TEM figures of graphite phase carbon nitride prepared by comparative example 1；
Fig. 2 is the Photocatalyzed Hydrogen Production performance map of graphite phase carbon nitride prepared by comparative example 1；
Fig. 3 is the TEM figures of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst prepared by embodiment 1；
Fig. 4 is the Photocatalyzed Hydrogen Production performance map of nitrogenous carbon quantum dot/graphite phase carbon nitride prepared by embodiment 1；
Fig. 5 is the TEM figures of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst prepared by embodiment 2；
Fig. 6 is nitrogenous carbon quantum dot/graphite phase carbon nitride prepared by graphite phase carbon nitride, embodiment 2 prepared by comparative example 1
The XRD of composite photo-catalyst；
Fig. 7 is nitrogenous carbon quantum dot and nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst prepared by embodiment 2
Infrared spectrogram；
Fig. 8 is the Photocatalyzed Hydrogen Production performance map of nitrogenous carbon quantum dot/graphite phase carbon nitride prepared by embodiment 2.
Embodiment
Comparative example 1
2g urea is ground fully in agate mortar, is subsequently transferred to react in hydrothermal reaction kettle, reaction temperature 100
DEG C, reaction time 10h, after reaction completely, by reactant by filtering, dialysing and dry, obtain graphite phase carbon nitride solid；
Gained graphite phase carbon nitride solid is placed in excessive concentrated nitric acid into the 4h that flows back (backflow is abundant) again makes its surface band carboxyl, then
Excessive polyethylene glycol is added, continuing backflow 4h (backflow is abundant) makes its surface hydroxyl；Dialyse after 3h, add hydrophilic ionic
Liquid 1,3- dibutyl imidazoles chloro salt, using the method concentrate solution of rotary evaporation, the concentration for making graphite phase carbon nitride is
1g·L-1。
Fig. 1 is the TEM figures of graphite phase carbon nitride prepared by comparative example 1, and laminated structure is presented in graphite phase carbon nitride；
Fig. 2 be comparative example 1 prepare graphite phase carbon nitride in the case where simulate daylight source photochemical catalyzing generation hydrogen
Rate-time curve, it is seen that the speed of graphite phase carbon nitride photochemical catalyzing generation hydrogen is about 1.4 μm of olg-1·min-1(i.e. every gram of catalyst, the mole per minute that can be generated hydrogen, similarly hereinafter).
Embodiment 1
The weight/mass percentage composition of nitrogenous carbon quantum dot is the preparation of 5wt.% composite photo-catalyst
(1) preparation of nitrogenous carbon quantum dot
According to mass ratio 5 under nitrogen atmosphere protection:1, it is placed in a ball mill after glucose and glycine are well mixed
Sealing ball grinder in, mechanical ball mill 4h under room temperature (25 DEG C, similarly hereinafter), rotating speed 580rpm, ratio of grinding media to material 20:1, agate used
A diameter of 5mm of ball；
After ball milling terminates, product is subjected to fully washing, high speed centrifugation and dialysis and operated, centrifugal rotational speed 10000rpm,
Dialysis time is 3h, then the nitrogenous carbon quantum dot solution rotating evaporation solvent by gained, and nitrogenous carbon quantum dot is made；
Above-mentioned nitrogenous carbon quantum dot is flowed back 4h in excess, concentrated nitric acid that Solute mass fraction is 73%, makes its table
Face takes carboxyl, then at the SOCl of excess2Carbon tetrachloride solution in flow back 10h, by the carboxylic of nitrogenous carbon quantum dot surface institute band
Base is converted to acid chloride groups, filtering, washing, is subsequently added into hydrophilic ionic-liquid 1,3- dibutyl imidazoles chloro salt, using rotation
The nitrogenous carbon quantum dot solution of method concentration to its concentration for turning evaporation is 1gL-1；
(2) under nitrogen protection, graphite phase carbon nitride solution prepared by 95mL comparative examples 1 is placed in four-hole boiling flask, delayed
The slow nitrogenous carbon quantum dot solution that 5mL steps (1) are added dropwise and prepare, drips after being stirred fully, reacts 3h at 20 DEG C,
Realize that the acylation between the nitrogenous carbon quantum dot of graphite phase carbon nitride and surface rich in acid chloride groups of surface hydroxyl functionalization is anti-
Should, obtain nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst.
Fig. 3 is that the TEM of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst prepared by embodiment 1 schemes, graphite-phase
Laminated structure is presented in carbonitride, and nitrogenous carbon quantum dot is dispersed in graphite phase carbon nitride surface, the particle diameter of nitrogenous carbon quantum dot
About 3~5nm；
Fig. 4 is that nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst prepared by embodiment 1 is simulating daylight source
The rate-time curve of lower photochemical catalyzing generation hydrogen, it is seen that it is about 2.43 μ that the speed of water generation hydrogen, which is catalytically decomposed, in it
mol·g-1·min-1, with comparative example 1 prepare pure graphite phase carbon nitride compared with, generate the speed of hydrogen increase to it is original
1.74 again.
Embodiment 2
The weight/mass percentage composition of nitrogenous carbon quantum dot is the preparation of 50wt.% composite photo-catalyst
(1) preparation of nitrogenous carbon quantum dot
According to mass ratio 5 under nitrogen atmosphere protection:1, it is placed in a ball mill after glucose and glycine are well mixed
Sealing ball grinder in, mechanical ball mill 8h under room temperature (25 DEG C, similarly hereinafter), rotating speed 1000rpm, ratio of grinding media to material 60:1, agate used
A diameter of 20mm of Nao balls；
After ball milling terminates, product is subjected to fully washing, high speed centrifugation and dialysis and operated, centrifugal rotational speed 30000rpm,
Dialysis time is 20h, then the nitrogenous carbon quantum dot solution rotating evaporation solvent by gained, and nitrogenous carbon quantum dot is made；
Above-mentioned nitrogenous carbon quantum dot is flowed back 10h in excess, concentrated nitric acid that Solute mass fraction is 73%, makes its table
Face takes carboxyl, then at the SOCl of excess2Carbon tetrachloride solution in flow back 10 hours, by nitrogenous carbon quantum dot surface institute band
Carboxyl is converted to acid chloride groups (the nitrogenous carbon quantum dot for obtaining acid chloride groups functionalization), filtering, washing, add hydrophily from
Sub- liquid N- butyl-N- methylpyrrole dicyan amine salt, it is 1gL to be made into concentration-1Nitrogenous carbon quantum dot solution；
(2) under nitrogen protection, graphite phase carbon nitride solution prepared by 50mL comparative examples 1 is placed in four-hole boiling flask, delayed
The slow nitrogenous carbon quantum dot solution that 50mL steps (1) are added dropwise and prepare, drips after being stirred fully, is reacted at 20 DEG C
3h, realize the acylation between the nitrogenous carbon quantum dot of graphite phase carbon nitride and surface rich in acid chloride groups of surface hydroxyl functionalization
Reaction, obtains nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst.
Fig. 5 is that the TEM of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst prepared by embodiment 2 schemes, graphite-phase
Laminated structure is presented in carbonitride, and nitrogenous carbon quantum dot is dispersed in graphite phase carbon nitride surface, the particle diameter of nitrogenous carbon quantum dot
About 5nm；
Fig. 6 is nitrogenous carbon quantum dot/graphite-phase nitridation prepared by graphite phase carbon nitride prepared by comparative example 1 and embodiment 2
The XRD of carbon composite photocatalyst,
Nitrogenous carbon quantum dot has a diffraction maximum at 23 °, and this is due to disorderly arranged caused between carbon-coating；Stone
Black phase carbon nitride has two characteristic diffraction peaks, and strong diffraction maximum is at about 27 °, and weak diffraction maximum is at about 13 °, the diffraction at 13 °
Peak corresponds to (100) crystal face of s-triazine unit planar structure, and the strong peak at 27 ° corresponds to conjugation aromaticring stacking
(002) crystal face；After nitrogenous carbon quantum dot adds, the diffraction peak intensity of graphite phase carbon nitride decreases, and illustrates nitrogenous carbon amounts
The interlayer that the introducing of son point can reduce graphite phase carbon nitride stacks；
Fig. 7 is the nitrogenous carbon quantum dot and nitrogenous carbon quantum dot/graphite-phase nitrogen of acid chloride groups functionalization prepared by embodiment 2
Change the infrared spectrogram of carbon composite photocatalyst, compared with the nitrogenous carbon quantum dot of acid chloride groups functionalization, nitrogenous carbon quantum dot/
The infrared figure of graphite phase carbon nitride composite photo-catalyst is located at 744 and 589cm-1The C-Cl peaks at place disappear, and illustrate nitrogenous carbon quantum
Chemically reacted between the acid chloride groups on point surface and the hydroxyl on graphite phase carbon nitride surface.
Fig. 8 is that nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst prepared by embodiment 2 is simulating daylight source
The rate-time curve of lower photochemical catalyzing generation hydrogen, it is seen that it is about 8.45 μ that the speed of water generation hydrogen, which is catalytically decomposed, in it
mol·g-1·min-1。
Claims (7)
- A kind of 1. preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst, it is characterised in that：Described system Preparation Method is, using glucose and glycine as carbon matrix precursor and nitrogen presoma, nitrogenous carbon quantum dot is synthesized using high speed ball-milling method； Graphite phase carbon nitride is made using hydro-thermal method；Using hydrophilic ionic-liquid as solvent, by acylation reaction by nitrogenous carbon quantum dot It is combined with graphite phase carbon nitride, prepares nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst, nitrogenous carbon quantum dot Pass through Covalent bonding together with graphite phase carbon nitride.
- 2. the preparation method of composite photo-catalyst as claimed in claim 1, it is characterised in that：Described nitrogenous carbon quantum dot/ In graphite phase carbon nitride composite photo-catalyst, the weight/mass percentage composition of nitrogenous carbon quantum dot is 5wt.%~50wt.%.
- 3. the preparation method of composite photo-catalyst as claimed in claim 1, it is characterised in that：In the synthesis of nitrogenous carbon quantum dot During, the mechanical ball mill time is 0.5~8h, and rotating speed is 580~1000rpm, ratio of grinding media to material 20:1~60:1, agate ball used A diameter of 5~20mm.
- 4. the preparation method of composite photo-catalyst as claimed in claim 1, it is characterised in that：The reaction temperature of the hydro-thermal method For 80~220 DEG C, the reaction time is 2~20h.
- 5. the preparation method of composite photo-catalyst as claimed in claim 1, it is characterised in that：Described hydrophilic ionic-liquid Including 1,3- dibutyl imidazoles chloros salt, N- butyl-N- methylpyrrole dicyan amine salt or 1- butyl -3- methylimidazole biphosphates Salt.
- 6. the preparation method of composite photo-catalyst as claimed in claim 1, it is characterised in that：Nitrogenous carbon quantum dot/graphite-phase When nitrogenizing carbon composite photocatalyst using acylation reaction preparation, by reflux operation, nitrogenous carbon quantum dot surface is first set to take acyl Cl radical, then graphite phase carbon nitride surface is taken hydroxyl, nitrogenous carbon quantum dot/graphite-phase nitrogen is made finally by acylation reaction Change carbon composite photocatalyst.
- 7. the preparation method of composite photo-catalyst as claimed in claim 6, it is characterised in that：The time of the reflux operation is 4~24h.
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