CN105597807A - Preparation method of carbon nitride photocatalyst with sheet-shaped structure embedded with carbon nano particles - Google Patents
Preparation method of carbon nitride photocatalyst with sheet-shaped structure embedded with carbon nano particles Download PDFInfo
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- CN105597807A CN105597807A CN201610071006.7A CN201610071006A CN105597807A CN 105597807 A CN105597807 A CN 105597807A CN 201610071006 A CN201610071006 A CN 201610071006A CN 105597807 A CN105597807 A CN 105597807A
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- 239000011852 carbon nanoparticle Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title abstract description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 235000014633 carbohydrates Nutrition 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 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 description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- BNWPUUZJGBXAFM-UHFFFAOYSA-N azane oxalonitrile Chemical compound N.N#CC#N BNWPUUZJGBXAFM-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- 238000006471 dimerization reaction Methods 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000035876 healing Effects 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 230000029553 photosynthesis Effects 0.000 abstract description 2
- 238000010672 photosynthesis Methods 0.000 abstract description 2
- 238000004088 simulation Methods 0.000 abstract description 2
- 238000004887 air purification Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical group C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 101100001672 Emericella variicolor andG gene Proteins 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 241000949477 Toona ciliata Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000012869 ethanol precipitation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 230000000007 visual effect 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
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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
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of a carbon nitride photocatalyst with a sheet-shaped structure embedded with carbon nano particles. The preparation method comprises the following steps: mixing carbohydrate and a carbon nitride precursor in a mass ratio of (1-200)/10000; and heating a mixture to 500-650 DEG C in a temperature programming manner, and roasting for 1-3 hours, wherein the heating speed is controlled to be 1-7 DEG C/h. With the adoption of the carbon nitride photocatalyst prepared by the method, the visible light photocatalytic activity can be expanded to be 600nm, and the carbon nitride photocatalyst has an excellent photocatalytic performance; and the preparation method has the advantages of simplicity, widely available raw materials and low cost, and is suitable for the fields of photocatalytic environment healing, air purification, hydrogen and oxygen production realized by water decomposition, manual simulation of photosynthesis and the like.
Description
Technical field
The present invention relates to a kind of preparation method without metal photochemical catalyst with high efficiency photocatalysis performance, belong to energySource, environmental technology field.
Background technology
Along with the demand of energy and environment development, effectively utilize sunshine and carry out environment healing and provide cleanThe energy is more and more important. Utilize photocatalytic process to carry out the photosynthetic work of degradable organic pollutant and simulating nature circleWith being extensively studied in recent years. Wherein, develop efficient photochemical catalyst, particularly visible light photocatalysisAgent has important scientific value and economical, societal benefits. Current modal photochemical catalyst is mainly inorganic halfConductor material is as TiO2, ZnO etc., but its scope majority to photoresponse concentrates on ultraviolet light range. 2009Year, novel have being developed and having good photocatalysis performance without nitride metal carbon of graphite-phase.
Graphite-phase carbonitride (g-C3N4) there is relative narrower its light abstraction width of optical band gap (2.7eV) canReach 475nm. But its photocatalysis performance needs to be further improved. In order further to promote its photocatalysis performance,The primary problem solving is the semi-conductive band gap that further narrows, and makes it absorb the more visible ray of wide region; SecondlyBe the separation that promotes photogenerated charge, thereby reach the object that promotes photocatalysis efficiency. King's heart of University of Fuzhou recentlyMorning newspaper road the groups such as phenyl ring are incorporated into g-C3N4Thereby in expanded to a certain extent g-C3N4VisibleLight absorption. But its light abstraction width is to be further improved in addition.
Summary of the invention
The invention provides a kind of by the carbon nano-structured g-C of being directly embedded into3N4In, obtain novel upper embedding carbon nanometerThe g-C of grain3N4The high efficiency photocatalyst preparation method of hydridization. Embedding carbon nanoparticle in the laminated structure that the method obtainsThe carbonitride of son has the photocatalytic activity of degradable organic pollutant and water decomposition hydrogen manufacturing.
For achieving the above object, the present invention is by the following technical solutions:
In laminated structure, a preparation method for the carbonitride photochemical catalyst of embedding carbon nano-particles, comprises the steps:
I. the ratio that is (1-200)/10000 in mass ratio by carbohydrate and carbonitride precursor is mixed;
II. mixture temperature programming step I being obtained is carried out roasting to 500-650 DEG C, and programming rate is controlled at1-7 DEG C/h, roasting 1～3 hour.
Preparation method as above, preferably, described step I is for first carbohydrate being made to carbon nano-particles,Then carbon nano-particles and carbonitride precursor are mixed and made into mixture.
Preparation method as above, preferably, in described step I makes carbohydrate carbon nano-particlesStep comprises:
The organic amine that is 2～6 by carbohydrate and carbon number is according to mol ratio 1:(1～3) mix, addPolar solvent, in solution, the concentration of carbohydrate is 1mmol/L～1.0mol/L; Be heated to 140-180 DEG C alsoMaintain this temperature lower 20 minutes to 4 hours; After reaction finishes, reactant liquor is joined in ethanol and precipitated, fromThe heart, is dissolved in precipitation in water, then the aqueous solution is joined in ethanol and is precipitated again, repeats above-mentioned precipitation processAt least 3 times; The sediment obtaining, 50～80 DEG C of oven dry, obtains carbon nano-particles.
Preparation method as above, preferably, mixes carbon nano-particles in described step I with carbonitride precursorThe step of making mixture comprises:
The carbon nano-particles that step I is obtained is made into the aqueous solution that concentration is 1～100mg/mL, by this aqueous solutionJoin in carbonitride precursor, wherein the mass ratio of carbon nano-particles and carbonitride precursor is 0.01-0.1wt%.
Preparation method as above, preferably, described polar solvent is selected from: water, DMF,1-METHYLPYRROLIDONE, methyl-sulfoxide, oxolane and acetone.
Preparation method as above, preferably, the organic amine that described carbon number is 2～6 is selected from: ethamine,Aniline, ethylenediamine, phenylenediamine, urea, thiocarbamide, diethylenetriamine, triethylene tetramine and polyethylene polyamine andIts derivative.
Preparation method as above, preferably, described can being selected from by the little molecule of carbonization: glucose, amino acid,Citric acid, starch and derivative thereof.
Preparation method as above, preferably, described carbonitride precursor is selected from: melamine, cyanamid dimerization,Single cyanogen ammonia, urea, thiocarbamide and derivative thereof.
Preparation method as above, preferably, the sintering temperature of described Step II is 590-610 DEG C, speed heats upDegree is 1-5 DEG C/h.
Beneficial effect of the present invention is the following aspects:
(1) the upper embedding carbon nano-particles carbonitride photochemical catalyst that prepared by the inventive method is ultra-thin laminated structure,There is higher specific area, be conducive to bring into play catalytic action.
(2) carbon nano-particles and g-C in this catalyst3N4Combine. Graphite is by the sp with armaticity2AssortedThe material with carbon element of the carbon atom composition of changing, its band gap is 0eV. But its single carbon atom makes its chemical inertness, noBe suitable for further chemical modification. Carbon nano-particles is a kind of development in recent years New Type of Carbon nanostructured out, itsComprise carbon point and graphene quantum dot. Mainly by thering is the carbon core of graphite-structure and abundant surface functional group structureThe particle of the nanosized becoming, wherein functional group comprises, carboxyl, amino, epoxide group, acid amides group. ThisMake carbon nano-particles not only there is the structure of conjugation but also there is the functional group that can react. By carbon nano-particles and g-C3N4Be connected, because the conjugated structure of carbon particle can be expanded g-C effectively3N4Effective conjugate length, make bandGap narrows, thereby absorbs more visible rays; Can be extended to 600nm to visible light photocatalysis active. The opposing partyFace, carbon nano-particles can be used as a kind of electron acceptor, can effectively accept g-C3N4The light induced electron producing,Thereby reach the effective separation that promotes photogenerated charge. This can further promote g-C3N4Photocatalysis performance.
(3) preparation method of this catalyst is simple, material is easy to get, with low cost, be applicable to photocatalysis environment and controlThe fields such as more, air cleaning, water decomposition hydrogen manufacturing and oxygen, manual simulation's photosynthesis.
Brief description of the drawings
Fig. 1 a is the transmission electron microscope picture of the carbon nano-particle 1. prepared of embodiment 1 step.
Fig. 1 b is the size distribution plot of the carbon nano-particle 1. prepared of embodiment 1 step.
Fig. 1 c is the electromicroscopic photograph under the carbon nano-particle high power 1. prepared of embodiment 1 step.
Fig. 1 d is the carbonitride transmission electron microscope picture of the upper embedding carbon nano-particle 2. prepared of embodiment 1 step.
Fig. 1 e is the electromicroscopic photograph under the carbonitride high power of the upper embedding carbon nano-particle 2. prepared of embodiment 1 step.
Fig. 2 A is the carbon nano-particle transmission electron microscope picture that in embodiment 2,1. step obtains.
Fig. 2 B is the carbon nano-particle AFM pattern that in embodiment 2,1. step obtains.
Fig. 3 A is the transmission electron microscope picture of the sample 4 prepared of embodiment 3.
Fig. 3 B is the high-resolution-ration transmission electric-lens figure of the sample 4 prepared of embodiment 3.
Fig. 4 A is the XRD collection of illustrative plates of the carbonitride with different content carbon nano-particle prepared of embodiment 3.
Fig. 4 B is that the Fourier transformation of the carbonitride with different content carbon nano-particle prepared of embodiment 3 is infraredSpectrum.
Fig. 5 is that the UV, visible light of the carbonitride with different content carbon nano-particle prepared of embodiment 3 absorbs lightSpectrum.
Fig. 6 A is the transmission electron microscope picture that comparative example 1 obtains product.
Fig. 6 B is the Raman spectrum that comparative example 1 obtains product.
Fig. 6 C is the X ray diffracting spectrum that comparative example 1 obtains product.
Fig. 7 A is the speed that the photocatalytic water splitting of the sample 1-6 that records of experimental example 1 produces hydrogen.
Fig. 7 B is the stability result of the photochemical catalyst that records of experimental example 1.
Detailed description of the invention
Below in conjunction with instantiation, technical scheme of the present invention is described further:
Embodiment 1 prepares the carbonitride of embedding carbon nano-particle in laminated structure
1. the preparation of carbon nano-particle: in round-bottomed flask by the diethyl of the citric acid of 10mmol and 30mmolAlkene triamine mixes, and then round-bottomed flask is placed in to oil bath, is heated to 180 DEG C from room temperature, and at 180 DEG CKeep 30min. Then reaction bulb is taken out from oil bath, be naturally cooled to room temperature. Obtain yellow or orange-yellow liquidBody. To be cooled to room temperature, solution is slowly added drop-wise in 500ml ethanol, adularescent Precipitation, centrifugalCollect solid. Then by dissolution of solid (～0.5mL) in a small amount of water, use again until completely dissolved 50mLEthanol precipitation, 3 times so repeatedly, the solid of acquisition is dried at 70 DEG C. Obtain carbon nano-particle.
2. the carbonitride of synthetic upper embedding carbon nano-particle: the carbon nano-particle obtaining in is 1. dissolved in water and is preparedThe aqueous solution of 10mg/mL, gets the 0.5mL carbon nano-particle aqueous solution and joins and be equipped with in 10g urea crucible, willCrucible is placed in Muffle furnace and is heated to 550 DEG C and at 550 DEG C, keep 30 minutes with the speed of 5 DEG C/h,Then crucible is taken out from Muffle furnace to nature cooling, after temperature is down to room temperature, collect the solid obtaining.Productive rate is 20%.
Fig. 1 a is the transmission electron microscope picture of the carbon nano-particle 1. prepared of step, and in figure, dark color spots is carbon nanometerGrain.
Fig. 1 b is the size distribution plot of the carbon nano-particle 1. prepared of step.
Fig. 1 c is the electromicroscopic photograph under the carbon nano-particle high power 1. prepared of step, and the region of parallel stripes pattern isCrystalline state carbon nano-particle, can find out that carbon nano-particle has crystallinity and the carbonization structure of height.
Fig. 1 d is the carbonitride transmission electron microscope picture of the upper embedding carbon nano-particle that 2. obtains of step, shows through too highTemperature is processed rear urea thermal polycondensation and is formed the carbonitride with laminated structure.
Fig. 1 e is the electromicroscopic photograph under the carbonitride high power of the upper embedding carbon nano-particle that 2. obtains of step, forms parallelThe region of candy strip is crystalline state carbon nano-particle, illustrates and on carbonitride, combines crystalline state carbon nano-particle.
Embodiment 2 prepares the carbonitride of embedding carbon nano-particle in laminated structure
1. the preparation of carbon nano-particle: the citric acid of 1mmol is joined in the urea of 3mmol, and addThe water of 10mL is made into the aqueous solution, until completely dissolved, solution is transferred to 20mL and has tetrafluoroethene inner bagIn hydrothermal reaction kettle, after sealing, be heated 180 DEG C, and at 180 DEG C, maintain 4 hours. Band reaction is fallenTo room temperature, open reactor. Reactant liquor is added dropwise in 200mL ethanol, and adularescent precipitation generates, centrifugalRear collection solid, then be dissolved in the water of 0.2mL, repeatedly, by ethanol precipitation, repeat the solid of acquisition 3 timesFor carbon nano-particle, dry stand-by.
2. the carbonitride of synthetic upper embedding carbon nano-particle: the carbon nano-particle obtaining in is 1. dissolved in water and is preparedThe aqueous solution of 10mg/mL, gets the 0.9mL carbon nano-particle aqueous solution and joins and be equipped with in 10g thiocarbamide crucible, willCrucible is placed in Muffle furnace and is heated to 600 DEG C and at 600 DEG C, keep 30 minutes with the speed of 5 DEG C/h, soAfter crucible to be taken out from Muffle furnace to nature cooling, after temperature is down to room temperature, collect the solid obtaining. ProduceRate is 10%.
Fig. 2 A is the carbon nano-particle transmission electron microscope picture that 1. step obtains, and in figure, dark color spots is carbon nano-particle.Wherein upper left illustration is high-resolution-ration transmission electric-lens figure, and the region of parallel stripes pattern is crystalline state carbon nano-particle;Upper right illustration is the particle size distribution of carbon nano-particle, and its size is 2-10 nanometer.
Fig. 2 B is the carbon nano-particle AFM pattern that 1. step obtains, and in figure, white dot is carbon nanometerParticle, the height that wherein linear scan in figure shows carbon nano-particle is in 0.5-1.5 nanometer.
The pattern of the carbonitride of the upper embedding carbon nano-particle that 2. step obtained and spectral quality and embodiment 1 obtainProduct type seemingly.
Embodiment 3 prepares the carbonitride of embedding carbon nano-particle in laminated structure
5mg citric acid is joined in 10g urea, in crucible, mix, be then placed on horse notIn stove, with the heating rate lines of 2 DEG C/h, Muffle furnace is risen to 600 DEG C, then at 600 DEG C, keep 30 pointsClock, takes out crucible, collects solid sample after being down to room temperature, is designated as sample 4. Productive rate is 15%.
The addition that changes citric acid, adopts above same steps to obtain the carbonitride of different carbon contents, is respectivelySample 1,2,3,5,6. Each sample citric acid inventory (with the mass ratio of urea) is referring to table 1:
Table 1
| Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 | |
| Inventory | 0.00％ | 0.01％ | 0.03％ | 0.05％ | 0.07％ | 0.09％ |
Fig. 3 A is the transmission electron microscope picture of sample 4, and black lines is the crimped edge of carbonitride sheet.
Fig. 3 B is the high-resolution-ration transmission electric-lens figure of sample 4, and the visible parallel stripes pattern of circle part, illustrates nitrogenizeOn carbon, combine crystalline state carbon nano-particle.
Fig. 4 A is the XRD collection of illustrative plates with the carbonitride of different content carbon nano-particle, is followed successively by sample from top to bottomThe curve of product 1-6, wherein (100) and (002) corresponding to carbonitride in the diffraction maximum at 13.1 and 27.8 placesDiffraction maximum.
Fig. 4 B is the Fourier transformation infrared spectrum with the carbonitride of different content carbon nano-particle, from top to bottomBe followed successively by the curve of sample 1,3,4,5,6. Wherein at 3100-3500,1200-1600 and 810cm-1PlaceN-H, the eigen vibration peak of C-N and 5-triazine units.
Fig. 4 A, 4B prove that the product obtaining is carbonitride.
Fig. 5 is the ultraviolet-visible absorption spectroscopy with the carbonitride of different content carbon nano-particle, curve by down toOn counter sample 1-6 successively. The visible increase sample along with carbon content strengthens gradually in the absorption of visual field. Upper rightSide's illustration is sample appearance photo, visible along with the increase color sample of carbon content is deepened gradually.
Comparative example 1
2mg citric acid is joined in 10g urea, in crucible, mix, be then placed on horse notIn stove, with the heating rate line of 1 DEG C/h, Muffle furnace is risen to 200 DEG C, then crucible is taken out, wait to be down toAfter room temperature, collect solid product.
Fig. 6 A is the transmission electron microscope picture that obtains product, and dark color spots is carbon nano-particle, has no sheet nitrogen in figureChange carbon. Illustrate and while being heated to 200 DEG C, do not generate sheet carbonitride.
The pattern that Fig. 6 A upper right illustration is Fast Fourier Transform (FFT), wherein symmetrical spot shows carbon nano-particle crystalline substanceThe regularity of lattice structure, if unordered situation can not occur by spottiness; Right illustration is high-resolution-ration transmission electric-lensFigure, in figure, parallel stripes pattern shows that product is crystalline state carbon nano-particle; Bottom right illustration is carbon nano-particle chiVery little distribution map.
Fig. 6 B by the Raman spectrum of acquisition product, at the peak at 1323 and 1565 places corresponding to the D band of graphite-phase andG band, wherein the appearance of G band shows that carbon nano-particle has graphite-phase structure.
Fig. 6 C by the X ray diffracting spectrum of acquisition product. 28.2 and 40.6 occur diffraction maximums also prove obtainThe carbon nano-particle obtaining has crystalline texture.
Embodiment 4 prepares the carbonitride of embedding carbon nano-particle in laminated structure
2mg lysine is joined in 10g thiocarbamide, in crucible, mix, be then placed on horse notIn stove, with the heating rate line of 1 DEG C/h, Muffle furnace is risen to 600 DEG C, then at 600 DEG C, keep 30Minute, crucible is taken out, after being down to room temperature, collect solid product. Productive rate is 8%. The upper embedding carbon obtaining is receivedThe pattern of the carbonitride product of rice grain is similar with sample 4 prepared by spectral quality and embodiment 3.
Embodiment 5 prepares the carbonitride of embedding carbon nano-particle in laminated structure
8mg glucose is joined in 10g melamine, in crucible, mix, be then placed onIn Muffle furnace, with the heating rate line of 1 DEG C/h, Muffle furnace is risen to 650 DEG C, then at 650 DEG C, keep30 minutes, crucible is taken out, after being down to room temperature, collect solid sample. Productive rate is 10%. The upper embedding obtainingThe pattern of the carbonitride product of carbon nano-particle is similar with sample 4 prepared by spectral quality and embodiment 3.
On experimental example 1, be embedded with the photocatalytic water splitting hydrogen manufacturing experiment of the carbonitride of different content carbon nano-particle
The sample 1-6 that photochemical catalyst uses respectively embodiment 3 to prepare, experimental procedure is:
20mg photochemical catalyst is dispersed in the triethanolamine mixed solution of 200mL water and 30mL, utilizes lightDeposition process, under 300W xenon lamp in the Pt nanoparticle of photocatalyst surface deposition 1wt%. Then at 300WXenon lamp in conjunction with UV-420CUT optical filter, be greater than at wavelength under the visible ray of 420 nanometers and test, institute producesThe GC-2014C equipment thermal conductance detector of raw hydrogen utilization Shimadzu is realized real-time monitoring. Photocatalytic water splittingProduce the speed of hydrogen and the results are shown in Table 2 and Fig. 7 A. Fig. 7 B is the stability result of the photochemical catalyst of sample 4.
Table 2
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this areaArt personnel, the present invention can have change and change. All in the spirit and principles in the present invention, that does appointsWhat amendment, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a preparation method for the carbonitride photochemical catalyst of embedding carbon nano-particles in laminated structure, its feature existsIn, the method comprises the steps:
I. the ratio that is (1-200)/10000 in mass ratio by carbohydrate and carbonitride precursor is mixed;
II. mixture temperature programming step I being obtained is carried out roasting to 500-650 DEG C, and programming rate is controlled at1-7 DEG C/h, roasting 1～3 hour.
2. preparation method as claimed in claim 1, is characterized in that, described step I is for first by carbon hydrateThing is made carbon nano-particles, then carbon nano-particles and carbonitride precursor is mixed and made into mixture.
3. preparation method as claimed in claim 2, is characterized in that, in described step I by carbohydrateThe step of making carbon nano-particles comprises:
The organic amine that is 2～6 by carbohydrate and carbon number is according to mol ratio 1: mix (1～3), addsPolar solvent, in solution, the concentration of carbohydrate is 1.0mmol/L～1.0mol/L; Be heated to 140-180 DEG CAnd maintain this temperature lower 20 minutes to 4 hours; After reaction finishes, reactant liquor is joined in ethanol and is precipitated,Centrifugal, precipitation is dissolved in water, then the aqueous solution is joined in ethanol and precipitated again, repeat above-mentioned precipitationJourney at least 3 times; The sediment obtaining, 50～80 DEG C of oven dry, obtains carbon nano-particles.
4. preparation method as claimed in claim 2, is characterized in that, in described step I by carbon nano-particlesThe step that is mixed and made into mixture with carbonitride precursor comprises:
The carbon nano-particles that step I is obtained is made into the aqueous solution that concentration is 1～100mg/mL, by this aqueous solutionJoin in carbonitride precursor, wherein the mass ratio of carbon nano-particles and carbonitride precursor is 0.01-0.1wt%.
5. preparation method as claimed in claim 3, is characterized in that, described polar solvent is selected from: water, N, N-Dimethyl formamide, 1-METHYLPYRROLIDONE, methyl-sulfoxide, oxolane and acetone.
6. preparation method as claimed in claim 3, is characterized in that, what described carbon number was 2～6 is organicAmine is selected from: ethamine, aniline, ethylenediamine, phenylenediamine, urea, thiocarbamide, diethylenetriamine, triethylene tetramineWith polyethylene polyamine and derivative thereof.
7. the preparation method as described in any one in claim 1-6, is characterized in that, described can carbonization little pointSon is selected from: glucose, amino acid, citric acid, starch and derivative thereof.
8. the preparation method as described in any one in claim 1-6, is characterized in that, described carbonitride precursorBe selected from: melamine, cyanamid dimerization, single cyanogen ammonia, urea, thiocarbamide and derivative thereof.
9. the preparation method as described in any one in claim 1-6, is characterized in that, the roasting of described Step IIBurning temperature is 590-610 DEG C, and programming rate is 1-5 DEG C/h.
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