CN107376967B - 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 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000010439 graphite Substances 0.000 title claims abstract description 61
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 61
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000005917 acylation reaction Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000002608 ionic liquid Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis 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
- 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 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000000502 dialysis Methods 0.000 claims description 6
- 238000007306 functionalization reaction Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 229910006124 SOCl2 Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 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
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- -1 oxygen (sulphur) compound Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 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
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 239000007788 liquid Substances 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
- 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
- 239000004642 Polyimide Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 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
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 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
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011229 interlayer 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
- 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
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 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
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—
-
- 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
Abstract
The invention belongs to optic catalytic composite material technical fields, in particular to using glucose and glycine as carbon matrix precursor and nitrogen presoma, nitrogenous carbon quantum dot a kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst: 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 and graphite phase carbon nitride pass through Covalent bonding together.
Description
Technical field
The invention belongs to optic catalytic composite material technical field, in particular to a kind of nitrogenous carbon quantum dot/graphite-phase nitridation
The preparation method of carbon composite photocatalyst.
Background technique
Photocatalytic hydrogen production by water decomposition is converted into cleaning and highdensity hydrogen using water as raw material, by inexhaustible solar energy
Can, it was not only able to satisfy the energy demand of the mankind, but also free from environmental pollution, and had had become the best side for solving energy shortage and environmental pollution
One of method has good potentiality in new energy development field.Photolysis water hydrogen reaction is actually to betide half under light excitation
Hydrogen is made in one catalytic reduction reaction on conductor catalyst surface, light induced electron reductive water.
The ratio of visible light is about 43% in sunlight, therefore the key for establishing photocatalytic hydrogen production by water decomposition system is exploitation
High activity, photochemical catalyst environmental protection low price, can effectively absorb visible light and be easily recycled.Reported photochemical catalyst is main now
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 wire),
Metal composite, polymer (such as polyimides) and nano-sized carbon (such as carbon nanotubes, graphite oxide, graphene).Wherein, it receives
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 by favor.
Carbon quantum dot with semiconductor property have unique band structure, adjustable band gap, more energy subbands,
The advantages that strong visible light-responded ability, controllable partial size and environmental protection, electronics transfer phenomenon can be generated under excited by visible light, but
Less than 50 μm ol h of rate of pure carbon quantum dot photodissociation aquatic products hydrogen-1, relatively low.
Summary of the invention
The object of the present invention is to provide a kind of composite catalyst with good photocatalytic hydrogen production by water decomposition efficiency, in order to
Realize above-mentioned purpose, nitrogenous carbon quantum dot/graphite phase carbon nitride that the present invention has been constructed by acylation reaction with Covalent bonding together
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 pass through acylation reaction for nitrogenous carbon quantum dot and graphite phase carbon nitride
It combines, prepares nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst, thus nitrogenous carbon quantum dot and graphite-phase nitrogen
Change carbon and pass through Covalent bonding together,
In nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst, the mass percentage 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 revolving speed is 580~1000rpm,
Ratio of grinding media to material is 20:1~60:1, and the diameter of agate ball used is 5~20mm,
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, reflux behaviour is first passed through
Work makes nitrogenous carbon quantum dot surface take acid chloride groups, then graphite phase carbon nitride surface is made to take hydroxyl, finally by acylated anti-
Nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst should be made,
Return time be 4~for 24 hours.
Present invention has an advantage that by the ionic liquid with distinct chemical and physical property as molten in acylation reaction
Agent and catalyst overcome using the concentrated sulfuric acid bring when as catalyst and extract the disadvantages of separation is difficult；
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.
Detailed description of the invention
Fig. 1 is the TEM figure 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 nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst TEM figure 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 nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst TEM figure 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 diagram 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.
Specific embodiment
Comparative example 1
2g urea is ground sufficiently in the agate mortar, is subsequently transferred to react in hydrothermal reaction kettle, reaction temperature 100
DEG C, reaction time 10h after fully reacting, by reactant by suction filtration, dialysis and drying, obtains graphite phase carbon nitride solid；
Gained graphite phase carbon nitride solid, which is placed in excessive concentrated nitric acid the 4h that flows back (reflux is abundant), again makes its surface band carboxyl, then
Excessive polyethylene glycol is added, continuing reflux 4h (reflux is abundant) keeps its surface hydroxyl；It dialyses after 3h, hydrophilic ionic is added
Liquid 1,3- dibutyl imidazoles chloro salt make the concentration of graphite phase carbon nitride using the method concentrate solution of rotary evaporation
1g·L-1。
Fig. 1 is the TEM figure 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 rate that graphite phase carbon nitride photochemical catalyzing generates hydrogen is about 1.4 μm of olg-1·min-1(i.e. every gram of catalyst, the mole that can be generated hydrogen per minute, similarly hereinafter).
Embodiment 1
The mass percentage of nitrogenous carbon quantum dot is the preparation of the composite photo-catalyst of 5wt.%
(1) preparation of nitrogenous carbon quantum dot
According to mass ratio 5:1 under nitrogen atmosphere protection, glucose and glycine are uniformly mixed and are placed on a ball mill
Sealing ball grinder in, mechanical ball mill 4h under room temperature (25 DEG C, similarly hereinafter), revolving speed 580rpm, ratio of grinding media to material 20:1, agate used
The diameter of ball is 5mm；
After ball milling, product is sufficiently washed, high speed centrifugation and dialysis operation, centrifugal rotational speed 10000rpm,
Dialysis time is 3h, then resulting nitrogenous carbon quantum dot solution rotating is evaporated solvent, and nitrogenous carbon quantum dot is made；
Above-mentioned nitrogenous carbon quantum dot is flowed back 4h in the concentrated nitric acid that excessive, Solute mass fraction is 73%, makes its table
Face takes carboxyl, then at excessive SOCl2Carbon tetrachloride solution in flow back 10h, by the carboxylic of nitrogenous carbon quantum dot surface institute band
Base is converted to acid chloride groups, is filtered, washed, and is subsequently added into hydrophilic ionic-liquid 1,3- dibutyl imidazoles chloro salt, using rotation
It is 1gL that nitrogenous carbon quantum dot solution to its concentration, which is concentrated, in the method for turning evaporation-1；
(2) under nitrogen protection, graphite phase carbon nitride solution prepared by 95mL comparative example 1 is placed in four-hole boiling flask, is delayed
The slow nitrogenous carbon quantum dot solution that 5mL step (1) preparation is added dropwise, drips after being stirred sufficiently, reacts 3h at 20 DEG C,
Realize that graphite phase carbon nitride and the surface of surface hydroxyl functionalization are anti-rich in the acylation between the nitrogenous carbon quantum dot of acid chloride groups
It answers, obtains nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst.
Fig. 3 is nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst TEM figure prepared by embodiment 1, graphite-phase
Laminated structure is presented in carbonitride, and nitrogenous carbon quantum dot is dispersed in graphite phase carbon nitride surface, the partial size 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
Lower photochemical catalyzing generates the rate-time curve of hydrogen, it is seen that it is about 2.43 μ that it, which is catalytically decomposed water and generates the rate of hydrogen,
mol·g-1·min-1, with comparative example 1 prepare pure graphite phase carbon nitride compared with, generate hydrogen rate increase to it is original
1.74 again.
Embodiment 2
The mass percentage of nitrogenous carbon quantum dot is the preparation of the composite photo-catalyst of 50wt.%
(1) preparation of nitrogenous carbon quantum dot
According to mass ratio 5:1 under nitrogen atmosphere protection, glucose and glycine are uniformly mixed and are placed on a ball mill
Sealing ball grinder in, mechanical ball mill 8h under room temperature (25 DEG C, similarly hereinafter), revolving speed 1000rpm, ratio of grinding media to material 60:1, Ma used
The diameter of Nao ball is 20mm；
After ball milling, product is sufficiently washed, high speed centrifugation and dialysis operation, centrifugal rotational speed 30000rpm,
Dialysis time is 20h, then resulting nitrogenous carbon quantum dot solution rotating is evaporated solvent, and nitrogenous carbon quantum dot is made；
Above-mentioned nitrogenous carbon quantum dot is flowed back 10h in the concentrated nitric acid that excessive, Solute mass fraction is 73%, makes its table
Face takes carboxyl, then at excessive SOCl2Carbon tetrachloride solution in flow back 10 hours, by nitrogenous carbon quantum dot surface institute band
Carboxyl is converted to acid chloride groups (obtaining the functionalized nitrogenous carbon quantum dot of acid chloride groups), is filtered, washed, be added hydrophily from
Sub- liquid N- butyl-N- methylpyrrole dicyan amine salt, being made into concentration is 1gL-1Nitrogenous carbon quantum dot solution；
(2) under nitrogen protection, graphite phase carbon nitride solution prepared by 50mL comparative example 1 is placed in four-hole boiling flask, is delayed
The slow nitrogenous carbon quantum dot solution that 50mL step (1) preparation is added dropwise, drips after being stirred sufficiently, reacts at 20 DEG C
3h, the graphite phase carbon nitride for realizing surface hydroxyl functionalization and surface are rich in the acylation between the nitrogenous carbon quantum dot of acid chloride groups
Reaction, obtains nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst.
Fig. 5 is nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst TEM figure prepared by embodiment 2, graphite-phase
Laminated structure is presented in carbonitride, and nitrogenous carbon quantum dot is dispersed in graphite phase carbon nitride surface, the partial size 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 diagram of carbon composite photocatalyst,
Nitrogenous carbon quantum dot has a diffraction maximum at 23 °, this is because disorderly arranged caused between carbon-coating；Stone
There are two characteristic diffraction peaks for black phase carbon nitride, and strong diffraction maximum is at about 27 °, diffraction of the weak diffraction maximum at about 13 °, 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 is added, 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 functionalized nitrogenous carbon quantum dot of acid chloride groups and nitrogenous carbon quantum dot/graphite-phase nitrogen prepared by embodiment 2
The infrared spectrogram for changing carbon composite photocatalyst, compared with the functionalized nitrogenous carbon quantum dot of acid chloride groups, nitrogenous carbon quantum dot/
The infrared figure of graphite phase carbon nitride composite photo-catalyst is located at 744 and 589cm-1The peak C-Cl at place disappears, and illustrates nitrogenous carbon quantum
It is 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
Lower photochemical catalyzing generates the rate-time curve of hydrogen, it is seen that it is about 8.45 μ that it, which is catalytically decomposed water and generates the rate of hydrogen,
mol·g-1·min-1。
Claims (5)
1. a kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst, it is characterised in that: the system
Preparation Method is, using glucose and glycine as carbon matrix precursor and nitrogen presoma, synthesizes nitrogenous carbon quantum dot 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 surface with acid chloride group
The nitrogenous carbon quantum dot of group and surface hydroxyl functionalization graphite phase carbon nitride combine, and prepare nitrogenous carbon quantum dot/graphite-phase nitrogen
Change carbon composite photocatalyst, nitrogenous carbon quantum dot and graphite phase carbon nitride pass through Covalent bonding together；
The surface with the nitrogenous carbon quantum dot of acid chloride groups the preparation method comprises the following steps:
Nitrogenous carbon quantum dot flows back in excessive concentrated nitric acid, its surface is made to take carboxyl, then at excessive SOCl2Four chlorinations
It flows back in carbon solution, the carboxyl of nitrogenous carbon quantum dot surface institute band is converted into acid chloride groups, is filtered, washed, is subsequently added into parent
Aqueous ionic liquid is configured to nitrogenous carbon quantum dot solution；
The surface hydroxyl functionalization graphite phase carbon nitride the preparation method comprises the following steps:
Gained graphite phase carbon nitride solid, which is placed in excessive concentrated nitric acid reflux, sufficiently makes its surface band carboxyl, is subsequently added into excess
Polyethylene glycol, continue reflux sufficiently make its surface hydroxyl；After dialysis, hydrophilic ionic-liquid is added, using rotary evaporation
Method concentrate solution, obtain the graphite phase carbon nitride of surface hydroxyl functionalization；
The hydrophilic ionic-liquid include 1,3- dibutyl imidazoles chloro salt, N- butyl-N- methylpyrrole dicyan amine salt or
1- butyl -3- methylimidazole dihydric phosphate.
2. the preparation method of composite photo-catalyst as described in claim 1, it is characterised in that: the nitrogenous carbon quantum dot/
In graphite phase carbon nitride composite photo-catalyst, the mass percentage of nitrogenous carbon quantum dot is 5wt.%~50wt.%.
3. the preparation method of composite photo-catalyst as described in claim 1, it is characterised in that: in the synthesis of nitrogenous carbon quantum dot
In the process, the mechanical ball mill time is 0.5~8h, and revolving speed is 580~1000rpm, and ratio of grinding media to material is 20:1~60:1, agate ball used
Diameter be 5~20mm.
4. the preparation method of composite photo-catalyst as described in claim 1, it is characterised in that: the reaction temperature of the hydro-thermal method
It is 80~220 DEG C, the reaction time is 2~20h.
5. the preparation method of composite photo-catalyst as described in claim 1, it is characterised in that: the nitrogenous carbon quantum dot preparation
The time of middle reflux operation be 4~for 24 hours.
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