CN109201102A - A kind of Z-type hetero-junctions M-C3N4The preparation method of/CdS composite photo-catalyst - Google Patents
A kind of Z-type hetero-junctions M-C3N4The preparation method of/CdS composite photo-catalyst Download PDFInfo
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- CN109201102A CN109201102A CN201811200860.4A CN201811200860A CN109201102A CN 109201102 A CN109201102 A CN 109201102A CN 201811200860 A CN201811200860 A CN 201811200860A CN 109201102 A CN109201102 A CN 109201102A
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- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000005286 illumination Methods 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 12
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- 238000001035 drying Methods 0.000 claims description 10
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- 239000002923 metal particle Substances 0.000 claims description 9
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- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000013528 metallic particle Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
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- 238000006243 chemical reaction Methods 0.000 claims description 2
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- 230000001699 photocatalysis Effects 0.000 abstract description 23
- 239000003054 catalyst Substances 0.000 abstract description 21
- 238000000151 deposition Methods 0.000 abstract description 12
- 230000008021 deposition Effects 0.000 abstract description 12
- 229910052697 platinum Inorganic materials 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000002096 quantum dot Substances 0.000 abstract description 6
- 238000000224 chemical solution deposition Methods 0.000 abstract description 5
- 229910052737 gold Inorganic materials 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 147
- 239000001257 hydrogen Substances 0.000 description 57
- 229910052739 hydrogen Inorganic materials 0.000 description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 48
- 238000007146 photocatalysis Methods 0.000 description 17
- 238000006303 photolysis reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
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- 239000013078 crystal Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- 229940116367 cadmium sulfide Drugs 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 239000002808 molecular sieve Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of Z-type hetero-junctions M-C3N4The preparation method of/CdS composite photo-catalyst, comprising the following steps: porous g-C is synthesized by the method for urea thermal polymerization first3N4Nanometer sheet, then by the method for light deposition in g-C3N4Surface is previously deposited metal promoters M (Pt, Au, Ag) etc., synthesizes M (Pt, Au, Ag)-g-C3N4, CdS quantum dot is grown in its surface in situ finally by chemical bath deposition method, synthesizes M-C3N4/CdS.The present invention utilizes the chemical synthesis process of substep, realizes the Effective Regulation from TypeII to Z-type hetero-junctions composite catalyst model by selective deposition metal promoters.M-C prepared by the present invention3N4/ CdS and traditional TypeII type composite photo-catalyst M-CdS/C3N4Compare and shows more preferably photocatalytic water H2-producing capacity.
Description
Technical field
The invention belongs to photocatalytic hydrogen production by water decomposition technical fields, and in particular to a kind of Z-type hetero-junctions M-C3N4/ CdS is compound
The preparation method of photochemical catalyst.
Background technique
With the development of society, the mankind gradually promote the demand of the energy, but band while a large amount of fossil energy consumptions
The energy and environmental problem are come, in order to realize the sustainable development of human society, national governments and scientist are opening energetically
Send out and seek to produce the green approach of new energy.Currently, during photochemical catalyzing, the compound of photo-generate electron-hole is
Limit photocatalytic water hydrogen generation efficiency key factor, wherein hetero-junctions guiding electron hole separation, this be study at present it is most general
All over one of the technological means for being also most effective promotion photogenerated charge separation.It is usually right in order to improve the efficiency of photocatalysis hydrogen production
The catalysis material of synthesis proposes more requirements.
Z-type composite photo-catalyst is a kind of photocatalysis hydrogen production material with excellent properties, but most of composite catalyzings
The photoelectronic transfer of agent is all to defer to TypeII heterojunction model, i.e., there is electronics the semiconductor A of quality fine paper position to be transmitted to low lead
B with position, hole are transmitted to A of the high price with position with the B of position from low price, this largely weakens the oxidation of photogenerated charge
And reducing power；In order to retain the redox ability of electrons and holes, it is compound that the prior art has scholar to develop Z-type hetero-junctions
Photochemical catalyst.
It is compared with the composite catalyst of traditional TypeII type, the composite photo-catalyst of Z model structure is protected to the greatest extent
The redox ability for the electrons and holes for having stayed conduction band position and valence band position to generate, therefore there is more excellent photocatalytic
Energy.
The synthesis of Z-type composite photo-catalyst is often more complicated at present, especially enable metal it is stable there are two kinds
There is very big challenge among semiconductor.For this problem, this patent mainly uses substep synthetic method, by selecting in advance
Selecting property light deposition metal is in different catalyst surfaces further compound another semiconductor, to control the deposition of metal
Site plays effective regulation to the structure of composite photo-catalyst.
Summary of the invention
The purpose of the present invention is to provide a kind of Z-type hetero-junctions M-C3N4The preparation method of/CdS composite photo-catalyst utilizes
The chemical synthesis process of substep is realized by selective deposition metal promoters from TypeII to Z-type hetero-junctions complex light
The Effective Regulation of catalyst model, the Z-type hetero-junctions M-C of synthesis3N4/ CdS composite photo-catalyst is for table in photocatalysis elutriation hydrogen
Reveal excellent liberation of hydrogen effect.
To achieve the goals above, the invention provides the following technical scheme:
A kind of Z-type hetero-junctions M-C3N4The preparation method of/CdS composite photo-catalyst, the preparation method include following step
It is rapid:
1)g-C3N4Preparation
Utilize the synthesizing nano-porous g-C of the method for urea thermal polymerization3N4；
2)M-C3N4Preparation
By g-C obtained in step 1)3N4Powder is placed in a beaker, and deionized water is added, after ultrasonic disperse is uniform, is put into
In photocatalytic reaction device, it is added and sacrifices agent solution in beaker, obtain mixed liquor；Then a certain amount of metal is measured with liquid-transfering gun
Salting liquid is added in mixed liquor, obtains mixed solution one；Under illumination, which occurs reduction reaction, forms metal
Grain is deposited on g-C3N4Surface, obtain M-C after centrifuge washing is dry3N4；
3)M-C3N4The synthesis of/CdS
By M-C obtained in step 2)3N4, deionized water is added, ultrasonic disperse uniformly obtains M-C3N4Mixed liquor, then
To M-C3N4It is separately added into caddy, ammonium chloride, thiocarbamide and ammonium hydroxide in mixed liquor, gained mixed solution is stirred into certain time, until
CdS is in M-C3N4The growth response on surface is complete, obtains mixed solution two；
4)M-C3N4The cleaning of/CdS material
By the washing of mixed solution two obtained in step 3) to neutrality, it is then centrifuged for the precipitating of separation mixed solution two
Grain, obtains aqueous M-C3N4/ CdS particle；
5)M-C3N4The drying of/CdS material
By M-C aqueous in step 4)3N4/ CdS particle is dried to arrive M-C in a vacuum drying oven3N4/CdS。
In Z-type hetero-junctions M-C as described above3N4The preparation method of/CdS composite photo-catalyst, it is preferable that in step 2)
Metal salt solution is chloroplatinic acid, gold chloride or silver nitrate；
Preferably, when metal salt solution is chloroplatinic acid, it is deposited on g-C3N4Surface metal particle mutually should be Pt, M-
C3N4Represent Pt-C3N4, step 3), 4) and 5) in M-C3N4/ CdS represents Pt-C3N4/CdS；
When metal salt solution is gold chloride, it is deposited on g-C3N4Surface metal particle mutually should be Au, M-C3N4It represents
Au-C3N4, step 3), 4) and 5) in M-C3N4/ CdS represents Au-C3N4/CdS；
When metal salt solution is silver nitrate, it is deposited on g-C3N4Surface metal particle mutually should be Ag, M-C3N4It represents
Ag-C3N4, step 3), 4) and 5) in M-C3N4/ CdS represents Ag-C3N4/CdS。
In Z-type hetero-junctions M-C as described above3N4The preparation method of/CdS composite photo-catalyst, it is preferable that the step 1)
In, utilize the synthesizing nano-porous g-C of the method for urea thermal polymerization3N4Specific step is as follows: 10g urea is weighed, crucible is put into,
It is sintered in Muffle furnace, obtains nanoporous g-C3N4；
Preferably, the sintering temperature of the sintering processes in Muffle furnace is 400~600 DEG C, and sintering time is 3~5h；
Preferably, the sintering temperature in Muffle furnace is 500 DEG C, and sintering time is 3h.
In Z-type hetero-junctions M-C as described above3N4The preparation method of/CdS composite photo-catalyst, it is preferable that institute in step 2)
The sacrifice agent stated is methanol；
Preferably, the additional amount of methanol is 1~2ml.
In Z-type hetero-junctions M-C as described above3N4The preparation method of/CdS composite photo-catalyst, it is preferable that in step 2)
The additional amount of the metal salt solution is g-C to be scaled corresponding metallic particles quality3N41~5%wt of powder quality.
In Z-type hetero-junctions M-C as described above3N4The preparation method of/CdS composite photo-catalyst, it is preferable that institute in step 3)
The molar ratio for stating caddy, ammonium chloride, thiocarbamide and ammonium hydroxide is 1: 2: (1~4): 10.
In Z-type hetero-junctions M-C as described above3N4The preparation method of/CdS composite photo-catalyst, it is preferable that institute in step 4)
Stating revolving speed when centrifuge separation is 10000r/min, centrifugation time 10min.
In Z-type hetero-junctions M-C as described above3N4The preparation method of/CdS composite photo-catalyst, it is preferable that step 2) and 3)
The amount of the deionized water of middle addition is 10~20ml.
In Z-type hetero-junctions M-C as described above3N4The preparation method of/CdS composite photo-catalyst, it is preferable that in step 5)
The drying temperature being dried in the vacuum oven is 60 DEG C, drying time 12h.
In Z-type hetero-junctions M-C as described above3N4The preparation method of/CdS composite photo-catalyst, it is preferable that institute in step 3)
The mixing time for stating mixed solution is 3~5h.
Compared with the immediate prior art, technical solution provided by the invention has following excellent effect:
The present invention uses step synthesis, is previously deposited metal on the surface of different catalyst using photo-reduction method,
Control has synthesized the C with different heterojunction models3N4/ CdS composite photo-catalyst.Wherein metal promoters respectively include platinum,
Gold is finally obtained with silver-colored three kinds of different source metals further using chemical bath deposition processes growth in situ cadmiumsulfide quantum dot
Pt-C3N4/CdS、Au-C3N4/CdS、Ag-C3N4/ CdS, which has, to be different from Type II heterojunction structure in conventional method and answers
Light combination catalyst.
Composite photo-catalyst prepared by the present invention, through comparing H2-producing capacity, under visible light photograph, average hydrogen-producing speed point
It Wei not 31mmolg-1h-1、8.9mmolg-1h-1、5.3mmolg-1h-1, it is significantly better than corresponding metal promoters Type II type
The composite photo-catalyst of heterojunction structure.
Technical solution provided by the invention is a kind of composite catalyzing of easy metal deposit site regulation heterojunction model
Agent, the Z-type M-C with good photocatalysis performance3N4/ CdS and preparation method thereof, the preparation method are simply easily-synthesized.
Detailed description of the invention
Fig. 1 is the Pt-C of the embodiment of the present invention3N4/ CdS and Pt-CdS/C3N4XRD diagram；
Fig. 2 is the Pt-C of the embodiment of the present invention3N4/ CdS and Pt-CdS/C3N4Transmission electron microscope picture；
Fig. 3 is the M-C of the embodiment of the present invention3N4/ CdS and M-CdS/C3N4Photocatalytic water H2-producing capacity under visible light photograph
Comparison curves.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff's every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted
Under condition, the feature in embodiment and embodiment in the present invention be can be combined with each other.
Z-type hetero-junctions M-C provided by the invention3N4The preparation method of/CdS composite photo-catalyst is closed using the chemistry of substep
At method, realized by selective deposition metal promoters from Type II to Z-type heterojunction composite photocatalyst model
Effective Regulation.Composition principle is: synthesizing porous g-C by the method for urea thermal polymerization first3N4Then nanometer sheet passes through light
The method of deposition is in g-C3N4Surface is previously deposited metal promoters M (Pt, Au, Ag), synthesizes M (Pt, Au, Ag)-g-C3N4,
CdS quantum dot is grown in its surface in situ finally by chemical bath deposition method, is finally synthesizing M-C3N4/CdS.Z prepared by the present invention
Type hetero-junctions M-C3N4/ CdS is compared to Type II type hetero-junctions M-CdS/C3N4Composite photo-catalyst model has superior
Photocatalytic water H2-producing capacity.
A kind of Z-type hetero-junctions M-C provided by the invention3N4The preparation method of/CdS composite photo-catalyst, preparation method include
Following steps:
1)g-C3N4Preparation
Utilize the synthesizing nano-porous g-C of the method for urea thermal polymerization3N4；
2)M-C3N4Preparation
By g-C obtained in step 1)3N4Powder is placed in a beaker, and deionized water is added, after ultrasonic disperse is uniform, is put into
In photocatalytic reaction device, it is added and sacrifices agent solution in beaker, obtain mixed liquor；Then a certain amount of metal is measured with liquid-transfering gun
Salting liquid is added in mixed liquor, obtains mixed solution one；Under illumination, which occurs reduction reaction, forms metal
Grain is deposited on g-C3N4Surface, obtain M-C after centrifuge washing is dry3N4；
3)M-C3N4The synthesis of/CdS
By M-C obtained in step 2)3N4, deionized water is added, ultrasonic disperse uniformly obtains M-C3N4Mixed liquor, then
To M-C3N4It is separately added into caddy, ammonium chloride, thiocarbamide and ammonium hydroxide in mixed liquor, gained mixed solution is stirred into certain time, until
CdS is in M-C3N4The growth response on surface is complete, obtains mixed solution two；
4)M-C3N4The cleaning of/CdS material
By the washing of mixed solution two obtained in step 3) to neutrality, it is then centrifuged for the precipitating of separation mixed solution two
Grain, obtains aqueous M-C3N4/ CdS particle；
5)M-C3N4The drying of/CdS material
By M-C aqueous in step 4)3N4/ CdS particle is dried to arrive M-C in a vacuum drying oven3N4/CdS。
In a specific embodiment of the present invention, further preferably, the metal salt solution in step 2) is chloroplatinic acid, gold chloride
Or silver nitrate；
Preferably, when metal salt solution is chloroplatinic acid, it is deposited on g-C3N4Surface metal particle mutually should be Pt, M-
C3N4Represent Pt-C3N4, step 3), 4) and 5) in M-C3N4/ CdS represents Pt-C3N4/CdS；
When metal salt solution is gold chloride, it is deposited on g-C3N4Surface metal particle mutually should be Au, M-C3N4It represents
Au-C3N4, step 3), 4) and 5) in M-C3N4/ CdS represents Au-C3N4/CdS；
When metal salt solution is silver nitrate, it is deposited on g-C3N4Surface metal particle mutually should be Ag, M-C3N4It represents
Ag-C3N4, step 3), 4) and 5) in M-C3N4/ CdS represents Ag-C3N4/CdS。
In a specific embodiment of the present invention, further preferably, it in step 1), is received using the method synthesis of urea thermal polymerization
Meter Duo Kong g-C3N4Specific step is as follows: weighing 10g urea, is put into crucible, be sintered in Muffle furnace, is received
Meter Duo Kong g-C3N4；
Preferably, the sintering temperature of the sintering processes in Muffle furnace be 400~600 DEG C (such as 420 DEG C, 440 DEG C, 450
DEG C, 460 DEG C, 480 DEG C, 500 DEG C, 520 DEG C, 540 DEG C, 560 DEG C, 580 DEG C), sintering time be 3~5h (such as 3.2h, 3.4h,
3.6h,3.8h,4h,4.2h,4.4h,4.6h,4.8h)；
Preferably, the sintering temperature in Muffle furnace is 500 DEG C, and sintering time is 3h.
In a specific embodiment of the present invention, further preferably, the sacrifice agent in step 2) is methanol；
Preferably, the additional amount of methanol is 1~2ml (such as 1.2ml, 1.4ml, 1.6ml, 1.8ml, 2ml).
Preferably, the additional amount of methanol is 2ml.
In a specific embodiment of the present invention, further preferably, the additional amount of the metal salt solution in step 2) is to change
Calculating as corresponding metallic particles quality is g-C3N41~5%wt (such as 1.5%wt, 2%wt, 2.5%wt, 3% of powder quality
Wt, 3.5%wt, 4%wt, 4.5%wt).
In a specific embodiment of the present invention, further preferably, caddy in step 3), ammonium chloride, thiocarbamide and ammonium hydroxide
Molar ratio is 1: 2: (1~4): 10 (such as 1: 2: 1: 10,1: 2: 1.5: 10,1: 2: 2: 10,1: 2: 2.5: 10,1: 2: 3: 10,1:
2∶3.5∶10、1∶2∶4∶10)。
In a specific embodiment of the present invention, further preferably, the revolving speed in step 4) when centrifuge separation is 10000r/
Min, centrifugation time 10min.
In a specific embodiment of the present invention, further preferably, the amount of step 2) and 3) the middle deionized water being added is
10~20ml (such as 12ml, 14ml, 16ml, 18ml, 20ml).
In a specific embodiment of the present invention, further preferably, what is be dried in a vacuum drying oven in step 5) is dry
Dry temperature is 60 DEG C, drying time 12h.
In a specific embodiment of the present invention, further preferably, the mixing time of mixed solution is 3~5h in step 3)
(such as 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h).
In a specific embodiment of the present invention, further preferably, the photocatalytic reaction device used in step 2) is by north
The light source of Jing Bofeilai Science and Technology Ltd. production, the optical filter of additional 420nm.
Embodiment 1
The Z-type hetero-junctions M-C that specific embodiments of the present invention provide3N4The preparation method of/CdS composite photo-catalyst includes
Following steps:
1)g-C3N4Preparation
The urea for weighing 10g, is put into crucible, is sintered in 500 DEG C of Muffle furnace, and sintering time 3h is obtained
To nanoporous g-C3N4；
2)Pt-C3N4Preparation
By g-C obtained in step 1)3N4Powder is placed in a beaker, and 10ml deionized water is added, after ultrasonic disperse is uniform,
It is put into photocatalytic reaction device, 2ml methanol is added as agent solution is sacrificed in beaker, then liquid-transfering gun measures 20 microlitres
For chloroplatinic acid in above-mentioned mixed liquor, platinum accounts for g-C3N4The mass percent of powder is 5%, and the concentration of aqueous solution of chloroplatinic acid is
270mg/ml obtains mixed solution one；Under illumination, which occurs reduction reaction, forms metallic particles Pt and is deposited on
g-C3N4Surface, obtain Pt-C after centrifuge washing is dry3N4；
3)Pt-C3N4The synthesis of/CdS
By Pt-C obtained in step 2)3N4, 10ml deionized water is added, ultrasonic disperse uniformly obtains Pt-C3N4Mixing
Liquid, respectively to Pt-C3N4Caddy, ammonium chloride, thiocarbamide and ammonium hydroxide, molar ratio 1: 2: 2: 10 are added in mixed liquor to mix gained
It closes solution and stirs 3h, until CdS is in Pt-C3N4The growth response on surface is complete, obtains mixed solution two；
4)Pt-C3N4The cleaning of/CdS material
It is 7 or so by the washing of mixed solution two obtained in step 3) to neutral PH, is then centrifuged for separating precipitating therein
Particle, centrifugal rotational speed 10000r/min, centrifugation time 10min obtain aqueous Pt-C3N4/ CdS particle；
5)Pt-C3N4The drying of/CdS material
By Pt-C aqueous in step 4)3N4/ CdS particle is dried in a vacuum drying oven, and drying temperature is 60 DEG C, does
Dry 12h to get arrive Pt-C3N4/CdS。
By Z-type hetero-junctions Pt-C obtained in the present embodiment3N4/ CdS composite photo-catalyst carries out X-ray powder diffraction,
And simultaneously to Pt-C3N4X-ray powder diffraction is carried out with CdS, obtained XRD diffracting spectrum is compared, as shown in Figure 1,
Pt-C3N4The crystal diffraction peak and Pt-C of/CdS3N4Corresponding with the crystal diffraction peak of CdS, the appearance at free from admixture peak illustrates Pt-
C3N4Good composite catalyst is formd with both CdS.
By Z-type hetero-junctions Pt-C obtained in the present embodiment3N4/ CdS composite photo-catalyst carries out transmission electron microscope analysis,
As shown in Fig. 2, showing C in projection electron microscope3N4With CdS it is compound after, C3N4Porous structure effectively prevent CdS quantum dot
Reunite, the Pt-C of formation3N4/ CdS composite photo-catalyst favorable dispersibility.
By Z-type hetero-junctions Pt-C prepared by the present embodiment3N4The composite photo-catalyst of/CdS is used as photodissociation aquatic products hydrogen material,
Its photocatalysis performance is tested, the specific method is as follows:
Weigh the Pt-C of 50mg3N4/ CdS, ultrasonic disperse is in 200ml aqueous solution, and after being uniformly dispersed, 20ml lactic acid is added
It as agent solution is sacrificed, is put into photochemical reactor, Ar purging 20min is passed through under dark-state stirring and excludes air in reactor
Afterwards, circulating cooling water pump keeping body system's reaction temperature is opened at 20 DEG C or so, and opening light source 300W xenon lamp, (420nm optical filter removes
Remove ultraviolet portion), stir lower progress photocatalysis experiment.
During light-catalyzed reaction at regular intervals, the gas of 1ml is extracted from photo catalysis reactor with syringe, benefit
With the content of its hydrogen generated of gas chromatographic analysis.The vertical analysis instrument of chromatography model Zhejiang good fortune for analyzing gaseous product is limited
Company Fuli 9700 (Molecular sieve, TCD, Ar are carrier gas).
By Pt-C prepared by the present embodiment3N4Hydrogen output of/CdS the composite photo-catalyst at illumination 12h is fabricated to song
Line, the Pt-C as shown in a figure in Fig. 3, after illumination 12h3N4The hydrogen output of/CdS reaches 366mmolg-1。
Embodiment 2
The chloroplatinic acid in step 2) is changed to gold chloride in the present embodiment, metallic particles Au is deposited on g-C3N4Surface,
Au-C is obtained after centrifuge washing is dry3N4, other methods step is same as Example 1, and details are not described herein.
Method in the present embodiment by light deposition is in g-C3N4Surface be previously deposited metal promoters Au, then lead to
It crosses chemical bath deposition method and grows CdS quantum dot in its surface in situ, synthesized Au-C3N4/CdS。
By prepared Z-type hetero-junctions Au-C3N4The composite photo-catalyst of/CdS is used as photodissociation aquatic products hydrogen material, tests it
It is identical in photocatalysis performance, specific method and embodiment 1, by Au-C prepared by the present embodiment3N4/ CdS composite photo-catalyst exists
Hydrogen output under illumination 12h is fabricated to curve, the Au-C as shown in the b figure in Fig. 3, after illumination 12h3N4The hydrogen output of/CdS
Reach 107mmolg-1。
Embodiment 3
The chloroplatinic acid in step 2) is changed to silver nitrate in the present embodiment, metallic particles Ag is deposited on g-C3N4Surface,
Ag-C is obtained after centrifuge washing is dry3N4, other methods step is same as Example 1, and details are not described herein.
Method in the present embodiment by light deposition is in g-C3N4Surface be previously deposited metal promoters Ag, then lead to
It crosses chemical bath deposition method and grows CdS quantum dot in its surface in situ, synthesized Ag-C3N4/CdS。
By prepared Z-type hetero-junctions Ag-C3N4The composite photo-catalyst of/CdS is used as photodissociation aquatic products hydrogen material, tests it
It is identical in photocatalysis performance, specific method and embodiment 1, by Ag-C prepared by the present embodiment3N4/ CdS composite photo-catalyst exists
Hydrogen output under illumination 12h is fabricated to curve, the Ag-C as shown in the c figure in Fig. 3, after illumination 12h3N4The hydrogen output of/CdS
Reach 63mmolg-1。
Embodiment 4
The temperature being sintered in Muffle furnace in step 1) in the present embodiment is 450 DEG C, sintering time 2h, other party
Method step is same as Example 1, and details are not described herein.
By Z-type hetero-junctions Pt-C prepared by the present embodiment3N4The composite photo-catalyst of/CdS is used as photodissociation aquatic products hydrogen material,
Test its photocatalysis performance, it is identical in specific method and embodiment 1, by Pt-C prepared by the present embodiment3N4/ CdS complex light is urged
Hydrogen output of the agent at illumination 12h is fabricated to curve (not shown), the Pt-C after illumination 12h3N4The hydrogen output of/CdS
Reach 350mmolg-1, illustrate Pt-C in 4 in embodiment3N4The hydrogen output of/CdS is lower than hydrogen output in embodiment 1, in embodiment 4
Change sintering temperature and sintering time influences whether Pt-C3N4The hydrogen output of/CdS.
Embodiment 5
The temperature being sintered in Muffle furnace in step 1) in the present embodiment is 550 DEG C, sintering time 4h, other party
Method step is same as Example 1, and details are not described herein.
By Z-type hetero-junctions Pt-C prepared by the present embodiment3N4The composite photo-catalyst of/CdS is used as photodissociation aquatic products hydrogen material,
Test its photocatalysis performance, it is identical in specific method and embodiment 1, by Pt-C prepared by the present embodiment3N4/ CdS complex light is urged
Hydrogen output of the agent at illumination 12h is fabricated to curve (not shown), the Pt-C after illumination 12h3N4The hydrogen output of/CdS
Reach 350mmolg-1, illustrate Pt-C in 5 in embodiment3N4The hydrogen output of/CdS is lower than hydrogen output in embodiment 1, in embodiment 5
Change sintering temperature and sintering time influences whether Pt-C3N4The hydrogen output of/CdS.
Embodiment 6
In the present embodiment in step 3), caddy, ammonium chloride, thiocarbamide and ammonium hydroxide molar ratio be 1: 2: 3: 10 other methods
Step is same as Example 1, and details are not described herein.
By Z-type hetero-junctions Pt-C prepared by the present embodiment3N4The composite photo-catalyst of/CdS is used as photodissociation aquatic products hydrogen material,
Test its photocatalysis performance, it is identical in specific method and embodiment 1, by Pt-C prepared by the present embodiment3N4/ CdS complex light is urged
Hydrogen output of the agent at illumination 12h is fabricated to curve (not shown), the Pt-C after illumination 12h3N4The hydrogen output of/CdS
Reach 330mmolg-1, illustrate Pt-C in 6 in embodiment3N4The hydrogen output of/CdS changes and implements lower than hydrogen output in embodiment 1
The proportion composition of raw material in example 6, to Pt-C3N4The hydrogen output of/CdS will cause influence, and the raw material proportioning in embodiment 1 is more excellent.
Embodiment 7
The additional amount of chloroplatinic acid is 10 microlitres in step 2) in the present embodiment, and platinum accounts for g-C3N4The quality percentage of powder
Than being 2.5%, other methods step is same as Example 1, and details are not described herein.
By Z-type hetero-junctions Pt-C prepared by the present embodiment3N4The composite photo-catalyst of/CdS is used as photodissociation aquatic products hydrogen material,
Test its photocatalysis performance, it is identical in specific method and embodiment 1, by Pt-C prepared by the present embodiment3N4/ CdS complex light is urged
Hydrogen output of the agent at illumination 12h is fabricated to curve (not shown), the Pt-C after illumination 12h3N4The hydrogen output of/CdS
Reach 310mmolg-1, Pt-C in embodiment 73N4The hydrogen output data of/CdS illustrate chlorine lower than hydrogen output data in embodiment 1
Platinic acid additional amount is to Pt-C3N4The hydrogen output of/CdS is affected, and additional amount is improper to reduce Pt-C3N4The hydrogen-separating quantity of/CdS,
Chloroplatinic acid additional amount in embodiment 1 is optimal.
Reference examples 1
This reference examples is used to prepare the TypeII type composite photo-catalyst Pt-CdS/C of different metal deposition site3N4, i.e. root
According to the preparation method of traditional TypeII type composite catalyst, in synthesis C3N4The composite catalyst surface light deposition metal of/CdS
Co-catalyst, specific steps are as follows:
First synthesize C3N4Platinum acid chloride solution is added before Photocatalyzed Hydrogen Production experiment in/CdS composite catalyst, carries out photo-reduction in situ
Platinum is deposited on the surface of composite catalyst, since cadmium sulfide conduction band position is lower than the conduction band position of three nitrogen four of carbon, according to traditional Type
II type structure, i.e. platinum are deposited on the surface of cadmium sulfide.
By TypeII type hetero-junctions Pt-CdS/C obtained in this reference examples3N4Composite photo-catalyst carries out x-ray powder
Diffraction, by the Pt-C in obtained XRD diffracting spectrum and embodiment 13N4/ CdS is compared, as shown in Figure 1, Pt-CdS/C3N4
Crystal diffraction peak and Pt-C3N4Corresponding with the crystal diffraction peak of CdS, the appearance at free from admixture peak illustrates the deposition site of Pt not
Influence the crystalline structure of composite photo-catalyst.
I.e. according to the preparation method of traditional TypeII type composite catalyst in this reference examples, in synthesis C3N4/ CdS's answers
Catalyst surface light deposition metal promoters are closed, by Type II type hetero-junctions Pt-CdS/C prepared by this reference examples3N4Answer
Light combination catalyst is used as photodissociation aquatic products hydrogen material, tests its photocatalysis performance, specific method and embodiment 1 are identical, this is compareed
Pt-CdS/C prepared by example3N4Composite photo-catalyst is fabricated to curve as shown in a in Fig. 3 in the hydrogen output under illumination 12h,
Pt-CdS/C after illumination 12h3N4Hydrogen output reach 117mmolg-1, Pt-C3N4/ CdS is Pt-CdS/C3N4Hydrogen output
3.1 again.
Reference examples 2
The difference of this reference examples and reference examples 1 is, by the chlorine platinum of addition before the experiment of the Photocatalyzed Hydrogen Production in synthesis step
Acid replaces with gold chloride, other steps are identical as reference examples 1, is urged with preparing the TypeII type complex light of different metal deposition site
Agent Au-CdS/C3N4。
By TypeII type hetero-junctions Au-CdS/C prepared by this reference examples3N4Composite photo-catalyst be used as photodissociation aquatic products hydrogen
Material tests its photocatalysis performance, and specific method and embodiment 1 are identical, by Au-CdS/C prepared by this reference examples3N4It is compound
Photochemical catalyst is fabricated to Au-CdS/C of the curve as shown in b in Fig. 3, after illumination 12h in the hydrogen output under illumination 12h3N4Production
Hydrogen amount reaches 37mmolg-1, Au-C3N4/ CdS is Au-CdS/C3N42.9 times of hydrogen output.
Reference examples 3
The difference of this reference examples and reference examples 1 is, by the chlorine platinum of addition before the experiment of the Photocatalyzed Hydrogen Production in synthesis step
Acid replaces with silver nitrate, other steps are identical as reference examples 1, is urged with preparing the TypeII type complex light of different metal deposition site
Agent Ag-CdS/C3N4。
By TypeII type hetero-junctions Ag-CdS/C prepared by this reference examples3N4Composite photo-catalyst be used as photodissociation aquatic products hydrogen
Material tests its photocatalysis performance, and specific method and embodiment 1 are identical, by Ag-CdS/C prepared by this reference examples3N4It is compound
Photochemical catalyst is fabricated to Ag-CdS/C of the curve as shown in c in Fig. 3, after illumination 12h in the hydrogen output under illumination 12h3N4Production
Hydrogen amount reaches 20mmolg-1, Ag-C3N4/ CdS is Ag-CdS/C3N43.2 times of hydrogen output.
By embodiment 1-7 and reference examples 1-3 it is found that the present invention passes through selectivity using the chemical synthesis process of distribution
Deposited metal co-catalyst realizes the Effective Regulation from Type II to Z-type heterojunction composite photocatalyst model, passes through control
The M-CdS/C synthesized in example3N4And the M-C of different metal deposition site prepared by the present invention3N4/ CdS is compared, and illustrates this hair
The Z-type heterojunction composite photocatalyst of bright preparation and traditional M-CdS/C3N4Material crystalline structure is identical, has more excellent
Photocatalysis water H2-producing capacity.
The composite catalyst different to both metal deposit sites has carried out the research of structure, pattern and performance, it was demonstrated that
Influence of the metal deposit site to light induced electron transmittance process and composite catalyst heterojunction structure.The obtained M- of the present invention
C3N4/ CdS and M-CdS/C3N4Compare and shows more preferably photocatalytic water H2-producing capacity.
Through comparing H2-producing capacity, under visible light photograph, Pt-C3N4/ CdS and Pt-CdS/C3N4, Au-C3N4/ CdS and Au-
CdS/C3N4, Ag-C3N4/ CdS and Ag-CdS/C3N4The composite catalyst of two kinds of different heterojunction structures, average hydrogen-producing speed point
It Wei not 31mmolg-1h-1And 9.8mmolg-1h-1, 8.9mmolg-1h-1And 3.1mmolg-1h-1, 5.3mmolg-1h-1With
1.6mmolg-1h-1。
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of Z-type hetero-junctions M-C3N4The preparation method of/CdS composite photo-catalyst, which is characterized in that the preparation method packet
Include following steps:
1)g-C3N4Preparation
Utilize the synthesizing nano-porous g-C of the method for urea thermal polymerization3N4；
2)M-C3N4Preparation
By g-C obtained in step 1)3N4Powder is placed in a beaker, and deionized water is added, after ultrasonic disperse is uniform, is put into light and urges
Change in reaction unit, is added and sacrifices agent solution in beaker, obtain mixed liquor；Then it is molten a certain amount of metal salt to be measured with liquid-transfering gun
Liquid is added in mixed liquor, obtains mixed solution one；Under illumination, which occurs reduction reaction, and it is heavy to form metallic particles
Product is in g-C3N4Surface, obtain M-C after centrifuge washing is dry3N4；
3)M-C3N4The synthesis of/CdS
By M-C obtained in step 2)3N4, deionized water is added, ultrasonic disperse uniformly obtains M-C3N4Mixed liquor, then to M-
C3N4It is separately added into caddy, ammonium chloride, thiocarbamide and ammonium hydroxide in mixed liquor, gained mixed solution is stirred into certain time, until CdS
In M-C3N4The growth response on surface is complete, obtains mixed solution two；
4)M-C3N4The cleaning of/CdS material
By the washing of mixed solution two obtained in step 3) to neutrality, it is then centrifuged for the precipitating particle of separation mixed solution two, is obtained
To aqueous M-C3N4/ CdS particle；
5)M-C3N4The drying of/CdS material
By M-C aqueous in step 4)3N4/ CdS particle is dried to arrive M-C in a vacuum drying oven3N4/CdS。
2. Z-type hetero-junctions M-C as described in claim 13N4The preparation method of/CdS composite photo-catalyst, which is characterized in that step
It is rapid 2) in metal salt solution be chloroplatinic acid, gold chloride or silver nitrate；
Preferably, when metal salt solution is chloroplatinic acid, it is deposited on g-C3N4Surface metal particle mutually should be Pt, M-C3N4It represents
Pt-C3N4, step 3), 4) and 5) in M-C3N4/ CdS represents Pt-C3N4/CdS；
When metal salt solution is gold chloride, it is deposited on g-C3N4Surface metal particle mutually should be Au, M-C3N4Represent Au-
C3N4, step 3), 4) and 5) in M-C3N4/ CdS represents Au-C3N4/CdS；
When metal salt solution is silver nitrate, it is deposited on g-C3N4Surface metal particle mutually should be Ag, M-C3N4Represent Ag-
C3N4, step 3), 4) and 5) in M-C3N4/ CdS represents Ag-C3N4/CdS。
3. Z-type hetero-junctions M-C as described in claim 13N4The preparation method of/CdS composite photo-catalyst, which is characterized in that institute
It states in step 1), utilizes the synthesizing nano-porous g-C of the method for urea thermal polymerization3N4Specific step is as follows: weighing 10g urea, puts
Enter crucible, be sintered in Muffle furnace, obtains nanoporous g-C3N4；
Preferably, the sintering temperature of the sintering processes in Muffle furnace is 400~600 DEG C, and sintering time is 3~5h；
Preferably, the sintering temperature in Muffle furnace is 500 DEG C, and sintering time is 3h.
4. Z-type hetero-junctions M-C as described in claim 13N4The preparation method of/CdS composite photo-catalyst, which is characterized in that step
It is rapid 2) described in sacrifice agent be methanol；
Preferably, the additional amount of methanol is 1~2ml.
5. Z-type hetero-junctions M-C as described in claim 13N4The preparation method of/CdS composite photo-catalyst, which is characterized in that step
It is rapid 2) in the additional amount of the metal salt solution be that be scaled corresponding metallic particles quality be g-C3N4The 1 of powder quality
~5%wt.
6. Z-type hetero-junctions M-C as described in claim 13N4The preparation method of/CdS composite photo-catalyst, which is characterized in that step
It is rapid 3) described in caddy, ammonium chloride, thiocarbamide and ammonium hydroxide molar ratio be 1: 2: (1~4): 10.
7. Z-type hetero-junctions M-C as described in claim 13N4The preparation method of/CdS composite photo-catalyst, which is characterized in that step
It is rapid 4) described in be centrifugated when revolving speed be 10000r/min, centrifugation time 10min.
8. Z-type hetero-junctions M-C as described in claim 13N4The preparation method of/CdS composite photo-catalyst, which is characterized in that step
The rapid amount 2) with 3) the middle deionized water being added is 10~20ml.
9. Z-type hetero-junctions M-C as described in claim 13N4The preparation method of/CdS composite photo-catalyst, which is characterized in that step
It is rapid 5) in the drying temperature that is dried in the vacuum oven be 60 DEG C, drying time 12h.
10. Z-type hetero-junctions M-C as described in claim 13N4The preparation method of/CdS composite photo-catalyst, which is characterized in that
The mixing time of mixed solution described in step 3) is 3~5h.
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