CN105498820A - Preparing method for high visible-light electron transfer Au/g-C3N4 supported photocatalytic material - Google Patents
Preparing method for high visible-light electron transfer Au/g-C3N4 supported photocatalytic material Download PDFInfo
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- CN105498820A CN105498820A CN201510926497.4A CN201510926497A CN105498820A CN 105498820 A CN105498820 A CN 105498820A CN 201510926497 A CN201510926497 A CN 201510926497A CN 105498820 A CN105498820 A CN 105498820A
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 21
- 230000027756 respiratory electron transport chain Effects 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 17
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 17
- 238000012546 transfer Methods 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005286 illumination Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910052724 xenon Inorganic materials 0.000 claims description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 abstract 1
- 230000032900 absorption of visible light Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 abstract 1
- 238000013032 photocatalytic reaction Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000011550 stock solution Substances 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 55
- 239000003054 catalyst Substances 0.000 description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 7
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
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- 230000004298 light response Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
Abstract
The invention relates to the field of material preparation and photocatalysis, and aims at providing a preparing method for a high visible-light electron transfer Au/g-C3N4 supported photocatalytic material. The method comprises the three steps that g-C3N4 is prepared through a precursor pyrolyzing and polymerizing method, a AuCl3.HCl.4H2O stock solution is prepared, and Au/g-C3N4 is prepared through a photo-reduction deposition method. According to the method, the prepared g-C3N4 is of a layered structure and has a large specific surface area and an appropriate energy gap. Au in the photocatalytic material obtained through the method is uniformly dispersed on the surface of a carrier. On one hand, Au serving as a promoter can promote complete separation of photoproduced electron holes and provide reaction activity sites; on the other hand, absorption of visible light can be promoted through the SPR effect of Au, and finally the photo-catalytic reaction effect can be improved.
Description
Technical field
The present invention is that one has comparatively high visible electro transfer Au/g-C
3n
4loaded photocatalyst preparation method, belongs to material preparation and photocatalysis field.
Background technology
Along with expanding economy and social progress, the demand of energy shortage and environmental pollution improvement is more and more eager, and environmental photocatlytsis technology is considered to a kind of low cost, eco-friendly green energy resource and environmental improvement technology, by extensive concern.Energy conversion and pollutant control are unified in photocatalysis electronic transfer process.Therefore develop there is high visible electron transfer capacity, the semiconductor catalyst of high visible catalytic reaction efficiency has self-evident economy and environment benefit.At present, the photochemical catalyst developed is a lot, but majority is ultraviolet light response catalyst.But sunshine medium ultraviolet light only accounts for 4%, in order to better utilize solar energy, exploitation visible light response catalyst has more realistic meaning.G-C
3n
4the photochemical catalyst being just found may be used for visible ray energy conversion and contaminant degradation in recent years, owing to there is the advantages such as cheap, high stability, unique photochemical properties and catalytic performance, g-C
3n
4obtain and study widely.But, simple g-C
3n
4there is the problems such as electron-hole recombination rate is high, interface electron transmission efficiency is low.G-C is improved by modification technology
3n
4photocatalysis performance there is good Research Significance.If patent CN103272639A is presoma with urea, by copolymerization to g-C
3n
4carry out modification, while strengthening catalyst surface mass transport process, reduce semiconductor band gap width, promote that photo-generated carrier is separated and migration, improve solar energy utilization ratio; Carbon nitrogen source precursor is fully mixed post-drying with inorganic salts by patent CN103301867A in aqueous, obtains the catalyst of inorganic ions doping, make g-C after calcining
3n
4photocatalytic activity significantly strengthen.Though above method increases specific surface area of catalyst, improves light-catalyzed reaction activity, fundamentally do not solve the high problem of electron-hole recombination rate.
Research shows, can promote effective separation of electron-hole with nano-noble metal material modifying semiconductor catalysis material, improves interface electron transmission efficiency, the service time of extending catalyst.After semiconductor catalyst area load nano metal material, because metal and semiconductor have different fermi levels, in light-catalyzed reaction process, semiconductor valence-band electrons is by conduction band extremely empty for induced transition, and because the effect of Fermi level, electronics finally will transit to fermi level, thus make partly to lead hole-electron to generation effectively separation, forming semiconductor valence band will based on hole, the system of Fermi level based on electronics; In photocatalytic process, the organic group (hydroxyl, carboxyl) being adsorbed onto semiconductor surface and valence band hole generation redox reaction and oxidized, simultaneously will accept the electronics that fermi level provides as the group of electron acceptor and be reduced, improving light-catalyzed reaction efficiency with this.The load of metal simultaneously can also improve the effective absorption of semiconductor catalyst to visible ray.Precious metals ag is loaded to nano-TiO by patent CN102764649A
2on, effective separation of electron hole pair can be promoted, improve electron transfer efficiency, also can strengthen its responding ability to visible ray simultaneously.
As SPR metal, Au supported catalyst obtains to be studied widely.On the one hand, Au, as co-catalyst, can promote the separation of electron hole pair, simultaneously for catalytic reaction provides avtive spot; On the other hand, the SPR effect of Au can expand visible absorption ability and the photocatalytic activity of catalyst.By certain catalyst preparing means, at g-C
3n
4upper load SPR metal A u, realizes efficent electronic transfer, has certain researching value.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the shortcoming that in prior art, high, the visible light-responded ability of catalyst electron-hole recombination rate in light-catalyzed reaction is weak, provides a kind of high visible electro transfer Au/g-C
3n
4the preparation method of load type photocatalytic material.The preparation of this catalyst adopts traditional photo-reduction sedimentation, and it is simple to operate, and the productive rate of synthesis is higher, is applicable to the requirement that extension is produced.
For technical solution problem, solution of the present invention is:
A kind of high visible electro transfer Au/g-C is provided
3n
4the preparation method of load type photocatalytic material, comprises the following steps:
(1) presoma thermal depolymerization legal preparation g-C
3n
4
The dicyanodiamine taking 2 ~ 10g, as carbon nitrogen source, puts into the crucible of adding a cover, and goes in Muffle furnace deammoniation of heating; Naturally, after cooling, grinding obtains faint yellow g-C
3n
4powder;
(2) storing solution is prepared
By the AuCl of 1g
3hCl4H
2o solid particle is dissolved in 100mL deionized water, and obtained concentration is the AuCl of 10mg/mL
3hCl4H
2o storing solution;
(3) photo-reduction sedimentation prepares Au/g-C
3n
4
By the g-C of 0.3g
3n
4powder adds in the mixed solution of 60mL deionized water and 15mL absolute methanol, then adds the AuCl of 130 ~ 3140 μ L
3hCl4H
2o storing solution, first stirs at dark condition lower magnetic force and makes Au in 2 hours
3+with g-C
3n
4abundant contact; Then illumination 3h, photoreduction adopts ultraviolet filter UVREF to make the emergent light spectrum wavelength of light source in 200 ~ 400nm scope; After reaction terminates, suction filtration with washed with de-ionized water three times, post-drying of spending the night under the air atmosphere of 60 DEG C, obtains high visible electro transfer Au/g-C
3n
4load type photocatalytic material.
In the present invention, the deammoniation of heating described in step (1) refers to: carbon nitrogen source is first raised to 500 DEG C with the speed of 10 DEG C/min by room temperature, constant temperature 2h in Muffle furnace; 520 DEG C are raised to again, constant temperature 2h with the speed of 5 DEG C/min; By this ammonia composition in process removing carbon nitrogen source of heating.
In the present invention, the light source described in step (3) is the xenon lamp of 300W.
In the present invention, in the course of reaction of step (3), continue logical Ar gas to get rid of O
2interference, and continuing magnetic force stir;
In the present invention, described high visible electro transfer Au/g-C
3n
4the specific area of load type photocatalytic material is 78 ~ 300m
2/ g, energy gap E
g=2.7eV.
Relative to prior art, the invention has the advantages that:
(1) the present invention to depolymerize the obtained g-C of method with forerunner's body heat
3n
4for layer structure, there is larger specific area (78 ~ 300m
2/ g) and suitable energy gap (E
g=2.7eV).
(2) in gained catalysis material of the present invention, Au is dispersed in carrier surface.Au can promote the separation completely of photo-generate electron-hole as co-catalyst and provide reactivity site on the one hand; The SPR effect of Au can promote the absorption of visible ray on the other hand, finally reaches the raising of light-catalyzed reaction effect.
Accompanying drawing explanation
Fig. 1 is the flow chart of the method for the invention;
Fig. 2 is g-C
3n
4and the Au/g-C of different Au load capacity
3n
4ultraviolet-visible diffuse reflection DRS scheme;
Fig. 3 is different g-C
3n
4and the Au/g-C of Au load capacity
3n
4pL figure;
Fig. 4 is g-C
3n
4and the Au/g-C of different Au load capacity
3n
4product hydrogen effect experimental figure;
Fig. 5 is g-C
3n
4and the Au/g-C of different Au load capacity
3n
4dechlorination effect lab diagram.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in more detail, and wherein part preparation condition is only the explanation as typical case, is not limitation of the invention.
Embodiment 1
1. photochemical catalyst Au/g-C
3n
4(0.2wt%) preparation
(1) g-C
3n
4preparation: adopt presoma thermal depolymerization legal.Take 2g dicyanodiamine and put into the crucible of adding a cover, in Muffle furnace, be first raised to 500 DEG C with the speed of 10 DEG C/min by room temperature, constant temperature 2h; 520 DEG C are raised to again, constant temperature 2h (deammoniation process) with the speed of 5 DEG C/min.Relief system naturally cool, obtain faint yellow g-C after grinding
3n
4powder.
(2) solution preparation: by 1g solid particle AuCl
3hCl4H
2o is dissolved in 100mL deionized water, the AuCl of obtained 10mg/mL concentration
3hCl4H
2o storing solution.
(3) Au/g-C
3n
4preparation: adopt photo-reduction sedimentation.The g-C of 0.3g
3n
4add in 60mL deionized water and 15mL absolute methanol, adding concentration is 10mg/mLAuCl
3hCl4H
2o storing solution 130 μ L, first stirs at dark condition lower magnetic force and makes Au in two hours
3+with g-C
3n
4abundant contact.Then illumination 3h, photoreduction light source used is the xenon lamp of 300W, adopts ultraviolet filter UVREF to make outgoing spectral wavelength 200 ~ 400nm scope.Logical Ar gas is continued in course of reaction, and continuous magnetic agitation.Suction filtration, washed with de-ionized water three times, oven dry of spending the night under 60 DEG C of air atmospheres, obtains high visible electro transfer Au/g-C
3n
4load type photocatalytic material.
Embodiment 2
1. photochemical catalyst Au/g-C
3n
4(0.5wt%) preparation
(1) g-C
3n
4preparation: adopt presoma thermal depolymerization legal.Take 4g dicyanodiamine and put into the crucible of adding a cover, in Muffle furnace, be first raised to 500 DEG C with the speed of 10 DEG C/min by room temperature, constant temperature 2h; 520 DEG C are raised to again, constant temperature 2h (deammoniation process) with the speed of 5 DEG C/min.Relief system naturally cool, obtain faint yellow g-C after grinding
3n
4powder.
(2) solution preparation: by 1g solid particle AuCl
3hCl4H
2o is dissolved in 100mL deionized water, the AuCl of obtained 10mg/mL concentration
3hCl4H
2o storing solution.
(3) Au/g-C
3n
4preparation: adopt photo-reduction sedimentation.The g-C of 0.3g
3n
4add in 60mL deionized water and 15mL absolute methanol, adding concentration is 10mg/mLAuCl
3hCl4H
2o storing solution 314 μ L, first stirs at dark condition lower magnetic force and makes Au in two hours
3+with g-C
3n
4abundant contact.Then illumination 3h, photoreduction light source used is the xenon lamp of 300W, adopts ultraviolet filter UVREF to make outgoing spectral wavelength 200 ~ 400nm scope.Logical Ar gas is continued in course of reaction, and continuous magnetic agitation.Suction filtration, washed with de-ionized water three times, oven dry of spending the night under 60 DEG C of air atmospheres, obtains high visible electro transfer Au/g-C
3n
4load type photocatalytic material.
Embodiment 3
1. photochemical catalyst Au/g-C
3n
4(1.0wt%) preparation
(1) g-C
3n
4preparation: adopt presoma thermal depolymerization legal.Take 5g dicyanodiamine and put into the crucible of adding a cover, in Muffle furnace, be first raised to 500 DEG C with the speed of 10 DEG C/min by room temperature, constant temperature 2h; 520 DEG C are raised to again, constant temperature 2h (deammoniation process) with the speed of 5 DEG C/min.Relief system naturally cool, obtain faint yellow g-C after grinding
3n
4powder.
(2) solution preparation: by 1g solid particle AuCl
3hCl4H
2o is dissolved in 100mL deionized water, the AuCl of obtained 10mg/mL concentration
3hCl4H
2o storing solution.
(3) Au/g-C
3n
4preparation: adopt photo-reduction sedimentation.The g-C of 0.3g
3n
4add in 60mL deionized water and 15mL absolute methanol, adding concentration is 10mg/mLAuCl
3hCl4H
2o storing solution 628 μ L, first stirs at dark condition lower magnetic force and makes Au in two hours
3+with g-C
3n
4abundant contact.Then illumination 3h, photoreduction light source used is the xenon lamp of 300W, adopts ultraviolet filter UVREF to make outgoing spectral wavelength 200 ~ 400nm scope.Logical Ar gas is continued in course of reaction, and continuous magnetic agitation.Suction filtration, washed with de-ionized water three times, oven dry of spending the night under 60 DEG C of air atmospheres, obtains high visible electro transfer Au/g-C
3n
4load type photocatalytic material.
Embodiment 4
1. photochemical catalyst Au/g-C
3n
4(2.0wt%) preparation
(1) g-C
3n
4preparation: adopt presoma thermal depolymerization legal.Take 8g dicyanodiamine and put into the crucible of adding a cover, in Muffle furnace, be first raised to 500 DEG C with the speed of 10 DEG C/min by room temperature, constant temperature 2h; 520 DEG C are raised to again, constant temperature 2h (deammoniation process) with the speed of 5 DEG C/min.Relief system naturally cool, obtain faint yellow g-C after grinding
3n
4powder.
(2) solution preparation: by 1g solid particle AuCl
3hCl4H
2o is dissolved in 100mL deionized water, the AuCl of obtained 10mg/mL concentration
3hCl4H
2o storing solution.
(3) Au/g-C
3n
4preparation: adopt photo-reduction sedimentation.The g-C of 0.3g
3n
4add in 60mL deionized water and 15mL absolute methanol, adding concentration is 10mg/mLAuCl
3hCl4H
2o storing solution 1256 μ L, first stirs at dark condition lower magnetic force and makes Au in two hours
3+with g-C
3n
4abundant contact.Then illumination 3h, photoreduction light source used is the xenon lamp of 300W, adopts ultraviolet filter UVREF to make outgoing spectral wavelength 200 ~ 400nm scope, illumination 3h.Logical Ar gas is continued in course of reaction, and continuous magnetic agitation.Suction filtration, washed with de-ionized water three times, oven dry of spending the night under 60 DEG C of air atmospheres, obtains high visible electro transfer Au/g-C
3n
4load type photocatalytic material.
Embodiment 5
1. photochemical catalyst Au/g-C
3n
4(5.0wt%) preparation
(1) g-C
3n
4preparation: adopt presoma thermal depolymerization legal.Take 10g dicyanodiamine and put into the crucible of adding a cover, in Muffle furnace, be first raised to 500 DEG C with the speed of 10 DEG C/min by room temperature, constant temperature 2h; 520 DEG C are raised to again, constant temperature 2h (deammoniation process) with the speed of 5 DEG C/min.Relief system naturally cool, obtain faint yellow g-C after grinding
3n
4powder.
(2) solution preparation: by 1g solid particle AuCl
3hCl4H
2o is dissolved in 100mL deionized water, the AuCl of obtained 10mg/mL concentration
3hCl4H
2o storing solution.
(3) Au/g-C
3n
4preparation: adopt photo-reduction sedimentation.The g-C of 0.3g
3n
4add in 60mL deionized water and 15mL absolute methanol, add the AuCl that concentration is 10mg/mL
3hCl4H
2o storing solution 3140 μ L, first stirs at dark condition lower magnetic force and makes Au in two hours
3+with g-C
3n
4abundant contact.Then illumination 3h, photoreduction light source used is the xenon lamp of 300W, adopts ultraviolet filter UVREF to make outgoing spectral wavelength 200 ~ 400nm scope, illumination 3h.Logical Ar gas is continued in course of reaction, and continuous magnetic agitation.Suction filtration, washed with de-ionized water three times, oven dry of spending the night under 60 DEG C of air atmospheres, obtains high visible electro transfer Au/g-C
3n
4load type photocatalytic material.
Performance test methods:
1) hydrogen effect experimental is produced
Take the self-control photo catalysis reactor that 0.05g catalyst sample puts into band circulation chuck, put into magnetic stir bar, add 35mL water and 15mL methyl alcohol successively.Be padded in the middle of quartz glass reactor cover and reactor by silicagel pad, at junction uniform application vacuum silicon grease, and at wound edgewise sealant tape, reactor sealed.Continue logical high-purity argon gas 1h from sample tap, air in reactor is drained.Afterwards rapidly with sealing gasket and raw material band sealing sample tap, and open light source.Testing light source used is 300W xenon lamp, and use VisREF (350-780nm) and Uvircut (400-780nm) optical filter to make outgoing spectral wavelength ranges be 400-780nm, light irradiates from top to bottom, and light intensity is 140mW/cm
2.Continue to pass into recirculated water, make the temperature of reaction system remain stable.The continuous magnetic agitation of whole course of reaction, makes sample be in suspended state always.Sample analysis per hour produces hydrogen concentration before turning on light and after turning on light.
2) dechlorination effect experiment
Take the self-control photo catalysis reactor (concentration of catalyst is 1g/L) that 0.15g catalyst sample puts into band circulation chuck, put into magnetic stir bar, add deionized water 100mL (logical N successively
2about 15 minutes), 2, the 4-chlorophenesic acid storing solution 600 μ L of methyl alcohol 50mL, 5g/L, make the initial concentration of 2,4-chlorophenesic acid be 20mg/L, magnetic agitation makes solution mix.Laboratory light source used is the xenon lamp of 300W, and [VisREF (350-780nm) and UVIRCUT (400-780nm) optical filter make outgoing spectral wavelength ranges be 400-780nm, and light irradiates from top to bottom to use visible ray.Continue to pass into recirculated water, make the temperature of reaction system remain stable.Logical N is continued in course of reaction
2, and continuous magnetic agitation.Adopt vacuum silicon grease to seal, sample time is 0,2,5,10,20,30,60,90,120,180,240,300min.The sample obtained disposable micropore filter (0.45 μm of poly (ether sulfone) film) (PES) filters, and adopts high performance liquid chromatography (HPLC) to analyze 2,4-chlorophenesic acid concentration.(3) test result explanation
To the high visible electro transfer Au/g-C of embodiment 1-5 gained
3n
4load type photocatalytic material carries out product hydrogen and dechlorination test by aforementioned properties method of testing, and its result as shown in Figure 4,5.
As can be seen from Figure 4, g-C is worked as
3n
4after load Au particle, produce hydrogen Be very effective and strengthen, and 1wt%Au/g-C
3n
4obtain best product hydrogen effect.When load capacity is for being less than 1wt%, along with the increase of Au load capacity, producing hydrogen effect and strengthening, providing avtive spot mainly due to Au as co-catalyst for reacting, the SPR effect of Au strengthens the absorption to visible ray in addition, finally causes the enhancing of photocatalytic activity.And when the load capacity of gold is greater than 1wt%, producing hydrogen effect declines, mainly because excessive Au is at g-C
3n
4surface aggregation, causes the active interface of the catalyst participating in reaction to reduce.。
As can be seen from Fig. 5 also, 1wt%Au/g-C is still
3n
4obtain best dechlorination effect.And when load capacity is less than 1wt%, along with the increase of Au load capacity, dechlorination effect strengthens, and is mainly that Au finally result in the enhancing of catalytic activity as co-catalyst and SPR effect; And when the load capacity of Au is greater than 1wt%, producing hydrogen effect declines, gather mainly due to Au the relation causing catalytic activity interface to be reduced.
Claims (5)
1. high visible electro transfer Au/g-C
3n
4the preparation method of load type photocatalytic material, is characterized in that, comprises the following steps:
(1) presoma thermal depolymerization legal preparation g-C
3n
4
The dicyanodiamine taking 2 ~ 10g, as carbon nitrogen source, puts into the crucible of adding a cover, and goes in Muffle furnace deammoniation of heating; Naturally, after cooling, grinding obtains faint yellow g-C
3n
4powder;
(2) storing solution is prepared
By the AuCl of 1g
3hCl4H
2o solid particle is dissolved in 100mL deionized water, and obtained concentration is the AuCl of 10mg/mL
3hCl4H
2o storing solution;
(3) photo-reduction sedimentation prepares Au/g-C
3n
4
By the g-C of 0.3g
3n
4powder adds in the mixed solution of 60mL deionized water and 15mL absolute methanol, then adds the AuCl of 130 ~ 3140 μ L
3hCl4H
2o storing solution, first stirs at dark condition lower magnetic force and makes Au in 2 hours
3+with g-C
3n
4abundant contact; Then illumination 3h, photoreduction adopts ultraviolet filter UVREF to make the emergent light spectrum wavelength of light source in 200 ~ 400nm scope; After reaction terminates, suction filtration with washed with de-ionized water three times, post-drying of spending the night under the air atmosphere of 60 DEG C, obtains high visible electro transfer Au/g-C
3n
4load type photocatalytic material.
2. method according to claim 1, is characterized in that, the deammoniation of heating described in step (1) refers to: carbon nitrogen source is first raised to 500 DEG C with the speed of 10 DEG C/min by room temperature, constant temperature 2h in Muffle furnace; 520 DEG C are raised to again, constant temperature 2h with the speed of 5 DEG C/min; By this ammonia composition in process removing carbon nitrogen source of heating.
3. method according to claim 1, is characterized in that, the light source described in step (3) is the xenon lamp of 300W.
4. method according to claim 1, is characterized in that, in the course of reaction of step (3), continues logical Ar gas to get rid of O
2interference, and continuing magnetic force stir.
5. method according to claim 1, is characterized in that, described high visible electro transfer Au/g-C
3n
4the specific area of load type photocatalytic material is 78 ~ 300m
2/ g, energy gap E
g=2.7eV.
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| CN106563499A (en) * | 2016-11-11 | 2017-04-19 | 重庆交通大学 | Melem/g-C3N4 composite material prepared through thermal polymerization, and preparation method and application thereof |
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