CN107262132A - A kind of sulfur doping g C3N4The preparation method of/zinc-cadmium sulfide composite photo-catalyst - Google Patents
A kind of sulfur doping g C3N4The preparation method of/zinc-cadmium sulfide composite photo-catalyst Download PDFInfo
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- CN107262132A CN107262132A CN201710619407.6A CN201710619407A CN107262132A CN 107262132 A CN107262132 A CN 107262132A CN 201710619407 A CN201710619407 A CN 201710619407A CN 107262132 A CN107262132 A CN 107262132A
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- zinc
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- catalyst
- cadmium sulfide
- cadmium
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- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 62
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 23
- 239000011593 sulfur Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 239000006104 solid solution Substances 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001661 cadmium Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 150000001298 alcohols Chemical group 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 4
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 3
- 238000011017 operating method Methods 0.000 abstract 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 23
- 229940043267 rhodamine b Drugs 0.000 description 23
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000004042 decolorization Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 235000013904 zinc acetate Nutrition 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940063190 flagyl Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- FPTPAIQTXYFGJC-UHFFFAOYSA-N metronidazole hydrochloride Chemical group Cl.CC1=NC=C([N+]([O-])=O)N1CCO FPTPAIQTXYFGJC-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the preparing technical field of new material, a kind of sulfur doping g C are specifically disclosed3N4/ zinc-cadmium sulfide composite photo-catalyst, preparation method is as follows：Certain mass thiocarbamide is taken to be placed in mortar after grinding, it is divided into two parts, thiocarbamide after a copy of it is ground is laid in crucible, then the zinc-cadmium sulfide precursor powder prepared is laid in thiocarbamide surface, another thiocarbamide after grinding is laid on zinc-cadmium sulfide precursor powder again, " sandwich " layer structure is formed；By above-mentioned " sandwich " layer structure, calcine under nitrogen protection, after product is cooled to room temperature, be ground to powder, obtain composite photo-catalyst.This method is that sulfur doping g C are prepared with one-step calcination method3N4/ zinc-cadmium sulfide composite photo-catalyst.This method technique is simple, with low cost, operating procedure is few, and equipment is easy to get and is easy to industrialization, and products obtained therefrom excellent performance has broad application prospects.
Description
Technical field
The present invention relates to the preparing technical field of new material, and in particular to a kind of sulfur doping g-C3N4/ zinc-cadmium sulfide complex light
The preparation method of catalyst.
Background technology
With economic and society fast development, energy crisis and environmental pollution are that two the worldwide of big urgent need to resolve are asked
Topic.Since Fujishima and Honda in 1972 is in TiO2Since photoelectrocatalysis decomposition aquatic products hydrogen and production oxygen are realized on electrode
(A.Fujishima, K.Honda, Nature 1972,238,37.), it is this solar energy to be directly changed into chemical energy
Technology is of great interest.And sunshine, condition can directly be utilized by having using semiconductor as the photocatalytic process of catalyst
Gently, reaction speed is fast, non-secondary pollution, the degradation of organic substances superior function such as thoroughly, is considered as a kind of and preferably solves the energy
With the effective means of environmental problem.Zinc-cadmium sulfide solid solution possesses regulatable band structure and band gap, therefore is that one kind has very much
The visible light responsive photocatalyst of potentiality.At present, many research groups successfully synthesize Zinc-cadmium sulfide photocatalyst, and study it
Photocatalytic activity is (such as：Q.Li,H.Meng,P.Zhou,Y.Zheng,J.Wang,J.G.Yu and J.R.Gong,ACS
Catal.2013,3,882-889；S.N.Garaje,S.K.Apte,S.D.Naik,J.D.Ambekar and B.B.Kale,
Environ.Sci.Technol.2013,47,6664-6672), however, single zinc-cadmium sulfide solid solution photo-generated carrier is answered
Close efficiency high and low to the utilization rate of light, cause catalytic activity relatively low.Accordingly, it would be desirable to be modified to it, improve photocatalysis and live
Property.
Research is found, the semiconductor that two kinds of band structures match is carried out being compounded to form hetero-junctions, can effectively suppress light
Being combined for raw electron-hole pair, is to improve one of effective ways of semiconductor light-catalyst performance.In recent years, g-C3N4Because of its system
The standby simple, advantageous property such as have suitable bandgap structure, visible light absorbing, chemical property and optical property stable, by wide
The extensive concern of big researcher, it is considered to be good semi-conducting material.To improve zinc-cadmium sulfide solid solution photoproduction current-carrying
The separative efficiency of son, g-C3N4It is commonly used to be combined with zinc-cadmium sulfide solid solution, is prepared into composite to strengthen catalyst pair
The absorption region of light and being combined for suppression photo-generated carrier.For example：Song etc. prepares g-C by simple calcination method3N4, and
It is added into the mixed solution of vulcanized sodium, caddy and zinc nitrate and carries out hydro-thermal reaction, finally prepares g-C3N4/CdxZn1- xS composite catalysts (Phys.Chem.Chem.Phys., 2015,17,29354--29362)；There is document report to pass through urine in the recent period
Element, thiocarbamide and zinc nitrate calcination by one-step method prepare g-C3N4/ ZnS composite catalysts (RSC Adv., 2016,6,17800-
17809).But, these methods exist high energy consumption, composite catalyst contain other impurities, experimental implementation process it is cumbersome and reaction
The problems such as time is long.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of experimental implementation simplicity, low energy consumption,
High-purity sulfur doping g-C can efficiently be prepared3N4The method of/zinc-cadmium sulfide composite photo-catalyst.It was found that by condition of nitrogen gas
The method of the thiocarbamide and zinc-cadmium sulfide presoma of next footwork calcining " sandwich " structure, can obtain high activity sulfur doping g-
C3N4/ zinc-cadmium sulfide composite photo-catalyst.
Realize that the object of the invention is adopted the technical scheme that：
A kind of thiocarbamide and zinc-cadmium sulfide presoma by one-step calcination " sandwich " structure prepares high activity sulfur doping g-
C3N4The preparation method of/zinc-cadmium sulfide composite photo-catalyst.Its step is as follows：
(1) zinc-cadmium sulfide precursor powder is prepared；
(2) take certain mass thiocarbamide to be placed in mortar after grinding, be divided into two parts, the thiocarbamide after a copy of it is ground
It is laid in crucible, the zinc-cadmium sulfide precursor powder prepared in step (1) is then laid in thiocarbamide surface, then will be another
Thiocarbamide after portion grinding is laid in zinc-cadmium sulfide precursor powder surface, forms " sandwich " layer structure；
(3) under nitrogen protection, by step (2) " sandwich " layer structure first at 400~500 DEG C calcining 0.1~
After 1h, it is warming up to 500~600 DEG C with 5 DEG C/min and continues to calcine 0.5-4h, be cooled to after room temperature, product is ground to powder,
Obtain composite photo-catalyst.
It is preferred that, it is under nitrogen protection, " sandwich " layer structure in step (2) is first at 500 DEG C in step (3)
Calcine after 0.5h, be warming up to 550 DEG C and continue to calcine 4h.
Further, the mass ratio of zinc-cadmium sulfide precursor powder and thiocarbamide is (1-2) in the step (2):(1-10),
Preferably (1.2-1.3):(1-8).
The preparation method of zinc-cadmium sulfide precursor powder comprises the following steps described in step (1)：
The first step, inorganic zinc salt and inorganic cadmium salt are added in solvent, stirring, obtain homogeneous transparent mixed solution A；Together
When, sulfurous organic compound is added in another container equipped with solvent, dispersed with stirring obtains homogeneous transparent solution B.
Second step, gained mixed solution A and solution B in the first step are mixed and to form mixed solution C, by solution C
In ultrasonic cleaning machine after 0.5~4h of ultrasonic disperse, solvent is rotated out with Rotary Evaporators, powder is obtained；
3rd step, the powder that second step is obtained is placed in mortar and is ground, and obtains zinc-cadmium sulfide precursor powder；
Further, the mol ratio of described inorganic zinc salt and inorganic cadmium salt is 1:0.1-9, preferably 1:1.
Further, the mol ratio of the summation and sulfurous organic compound of the inorganic zinc salt and inorganic cadmium salt addition is 1:1~
1:4, preferably 1:4.
Further, described inorganic zinc salt is the one or more in zinc chloride, zinc sulfate, zinc nitrate and zinc acetate.
Further, described inorganic cadmium salt is the one or more in caddy, cadmium sulfate, cadmium nitrate and cadmium acetate.
Further, described solvent is one kind in alcohols, acetone and water.
Further, the sulfurous organic compound is thiocarbamide.
The characterizing method of the micro-structural of composite catalyst prepared by the inventive method is：
(1) it is that x-ray source, sweep speed are 0.05 in Cu Ko·s-1X-ray diffractometer (HZG4/B-PC types) on
To X-ray diffraction (XRD) spectrogram determine crystalline phase.
(2) Tecnai G20 types transmission electron microscopes (TEM) are produced with the U.S. and Japan's production Hitachi S-4800 types are swept
Retouch electron microscope (SEM) and carry out sample topography observation.
(3) speed of photoactivation rhodamine B degradation dyestuff, flagyl and phenol respectively is obtained compound to assess
The photocatalytic activity of photochemical catalyst.
Compared with prior art, the advantages of the present invention are as follows：
This method technique is simple, easily operated, mild condition, energy consumption are low, thus with more practical implementation prospect；Institute
Catalyst without other impurities (visible XRD results), absorption property be good, active height, thus with broader practice prospect.
Brief description of the drawings
The sample CZS prepared in Fig. 1-embodiment 10.5- SCN-8 (Fig. 1 a) and CZS0.9- SCN-8 (Fig. 1 b) ESEM
Figure；
The sample CZS prepared in Fig. 2-embodiment 20.5(Fig. 2 a), SCN (Fig. 2 b) and CZS0.5- SCN-2 (Fig. 2 c) scanning
Electron microscope；
The sample CZS prepared in Fig. 3-embodiment 20.5(Fig. 3 a), SCN (Fig. 3 b), CZS0.5- SCN-2 (Fig. 3 c) transmission
Sem image, and CZS0.5- SCN-2 high-resolution-ration transmission electric-lens image (Fig. 3 d)；
Sample SCN, the CZS prepared in Fig. 4-embodiment 20.5、CZS0.5-SCN-1、CZS0.5-SCN-2、CZS0.5-SCN-4
And CZS0.5- SCN-5 powder x-ray diffraction spectrogram；
The sample CZS prepared in Fig. 5-embodiment 30.5- SCN-500 (Fig. 5 a), CZS0.5- SCN-550 (Fig. 5 b), CZS0.5-
SCN-600 (Fig. 5 c) scanning electron microscope (SEM) photograph.
Embodiment
Applicant is described in detail the method in conjunction with specific embodiments to the present invention below, so as to the skill of this area
Art personnel are further understood by the present invention, but following examples are not construed to the scope of the present invention in any way
Limitation.
Zinc acetate used is Zinc diacetate dihydrate in following examples.
Composite photo-catalyst naming rule prepared by following examples is：
(1) the sulfur doping g-C prepared3N4SCN is named as, solid solution is named as CZSx1, composite photo-catalyst is named as
CZSx1-SCN-x2, wherein x1Represent molecular formula in element Zn stoichiometric number, value be 0.1,0.2,0.3,0.4,0.5,0.6,
0.7th, 0.8 or 0.9.x2Represent the addition of the thiocarbamide during composite photo-catalyst is prepared, unit is g, value is 1,2,
4th, 5,6 or 8.
(2) composite photo-catalyst prepared under different calcining heats is named as CZSx1- SCN-Ty, wherein x1Represent solid solution
The stoichiometric number of Zn elements in body molecular formula, Ty represents the temperature of calcining, and unit is DEG C, value be 500,525,550,575 or
600。
Embodiment 1：Zinc source (n different with cadmium source mol ratioZn/nCd) composite photo-catalyst CZSx1-SCN-x2Preparation
(1) by mol ratio 1:9 zinc acetate and cadmium acetate is dissolved in 30mL absolute ethyl alcohols, is continuously stirred at room temperature
30min obtains solution A, and the integral molar quantity of zinc acetate and cadmium acetate is 2.5mmol；Meanwhile, 10mmol thiocarbamide is dissolved in separately
In outer 30mL absolute ethyl alcohols, stirring 30min obtains solution B at 60 DEG C.Solution A and B are mixed to form mixed solution
C, by solution C in ultrasonic cleaning machine after ultrasonic disperse 2h, then the mixed solution is transferred in Rotary Evaporators, in 80 DEG C of bars
Part backspin obtains powder after steaming whole absolute ethyl alcohols, places it in mortar and is ground, and obtains zinc-cadmium sulfide precursor
Last 1.26g.
(2) it is another to take 8g thiocarbamides to be placed in mortar after grinding, two parts are divided into, the thiocarbamide tiling after a copy of it is ground
In corundum crucible, then the 1.26g zinc-cadmium sulfide precursor powders that step (1) is obtained are laid in the thiocarbamide in corundum crucible
Another thiocarbamide after grinding, is finally laid on zinc-cadmium sulfide precursor powder by surface, forms " sandwich " layer structure,
Obtained " sandwich " layer structure is put into Muffle furnace, under nitrogen protection, first from room temperature to 500 DEG C of calcining 0.5h
Afterwards, 550 DEG C of calcining 4h are continuously heating to, heating rate is 5 DEG C/min, is cooled to after room temperature, product is ground into powder, i.e.,
Obtain CZS0.1- SCN-8 composite photo-catalysts.
According to above-mentioned preparation method, change the mol ratio of zinc acetate and cadmium acetate, according to the zinc acetate and vinegar in table 1 below
The mol ratio of sour cadmium prepares the composite photo-catalyst of zinc source and cadmium source different mol ratio.
Table 1
CZS is chosen to catalyst prepared by embodiment 10.5- SCN-8 and CZS0.9- SCN-8 is scanned through sem image point
Analysis, shown in such as Fig. 1 (a), Fig. 1 (b), it can be seen from figure 1 that when Zn moles are smaller in prepared composite photo-catalyst, zinc sulphide
Cadmium solid solution body portion is by sulfur doping g-C3N4(SCN) wrapped up, be partially dispersed in sulfur doping g-C3N4Surface, and zinc-cadmium sulfide
The particle size of solid solution is 0.5 μm or so；When Zn moles are larger in catalyst, zinc-cadmium sulfide solid solution is completely by sulfur doping
g-C3N4Wrapped up, and in sulfur doping g-C3N4Surface there is substantial amounts of gap structure.
Embodiment 2：Sulfur doping g-C3N4The different composite photo-catalyst CZS of content0.5-SCN-x2Preparation
(1) cadmium acetate of 1.25mmol zinc acetate and 1.25mmol is dissolved in 30mL absolute ethyl alcohols, held at room temperature
Continuous stirring 30min obtains solution A；Meanwhile, 10mmol thiocarbamide is dissolved in other 30mL absolute ethyl alcohols, stirred at 60 DEG C
30min obtains solution B, then, two kinds of solution of A and B is mixed to form mixed solution C, by solution C in ultrasonic cleaning machine
Middle ultrasonic disperse 2h, then the mixed solution is transferred in Rotary Evaporators, whole absolute ethyl alcohols are rotated out under the conditions of 80 DEG C
After obtain powder, place it in mortar and be ground, obtain zinc-cadmium sulfide precursor powder 1.28g.
(2) it is another to take 1g thiocarbamides to be placed in mortar after grinding, two parts are divided into, the thiocarbamide tiling after a copy of it is ground
In corundum crucible, then the 1.28g zinc-cadmium sulfide precursor powders that step (1) is obtained are laid in the thiocarbamide in corundum crucible
Another thiocarbamide after grinding, is finally laid on zinc-cadmium sulfide precursor powder by surface, forms " sandwich " layer structure,
Obtained " sandwich " layer structure is put into Muffle furnace, under nitrogen protection, first from room temperature to 500 DEG C of calcining 0.5h
Afterwards, 550 DEG C of calcining 4h are continuously heating to, heating rate is 5 DEG C/min, is cooled to after room temperature, product is ground into powder, i.e.,
Obtain CZS0.5- SCN-1 composite photo-catalysts.
According to above-mentioned preparation method, it is respectively 2g, 4g, 5g to change thiocarbamide addition in step (2), and other steps are not
Become, composite photo-catalyst is prepared respectively：CZS0.5-SCN-2、CZS0.5-SCN-4、CZS0.5-SCN-5。
Take 10g thiocarbamides to be transferred to after grinding in crucible, put it into Muffle furnace, 550 DEG C are warming up under nitrogen protection
4h is incubated, heating rate is 5 DEG C/min, is cooled to after room temperature, product is ground into powder, produce sulfur doping g-C3N4, name
For SCN.
According to CZS0.5The step of-SCN-1 composite photo-catalysts (1), prepares zinc-cadmium sulfide precursor powder, then by forerunner
Body powder under nitrogen protection, after elder generation is from room temperature to 500 DEG C of calcining 0.5h, is continuously heating to calcine 4h at 550 DEG C, heated up
Speed is 5 DEG C/min, after product is cooled to room temperature, is ground to powder, obtains solid solution CZS0.5。
Choose SCN, CZS0.5And CZS0.5- SCN-2 is scanned through Electronic Speculum sign, as a result as shown in Figure 2.As it is clear from fig. 2 that pure
CZS0.5The graininess of reunion, granular size 100-200nm (such as Fig. 2 a) are showed, SCN shows unordered sheet accumulation knot
Structure, and there is on SCN surfaces 10-100nm pore structure (such as Fig. 2 b), composite photo-catalyst CZS0.5CZS in-SCN-20.5Gu
Melt granules, which are loaded, is dispersed in SCN surface, and pore structure (such as Fig. 2 c) occurs on SCN surface.
Fig. 3 (a)-(c) is respectively CZS0.5、SCN、CZS0.5- SCN-2 images of transmissive electron microscope, Fig. 3 (d) is CZS0.5-
SCN-2 high-resolution-ration transmission electric-lens image, is further proved, CZS from Fig. 30.5Solid solution pellet is dispersed in SCN surface, and
CZS0.5It is in close contact between solid solution pellet and SCN.
SCN, CZS in embodiment 20.5And the X-ray diffraction spectrogram of each composite photo catalyst powder is as shown in Figure 4.From figure
4 is visible, CZS0.5Solid solution is hexagonal wurtzite structure, CZS0.5The diffraction maximum of solid solution is between ZnS and CdS, shows shape
Into CZS0.5Solid solution, and CZS in composite photo-catalyst0.5Exist with SCN diffraction maximum, illustrate both in composite catalyst
Material is stabilized.
Embodiment 3：Under different calcining heats, composite photo-catalyst CZS0.5- SCN-Ty preparation
In order to examine different calcining heats to preparing composite photo-catalyst CZS0.5-SCN-x2The influence of structure, has been carried out not
Synthermal lower calcining experiment.Except the thiocarbamide used in step (2) is 6g, the calcining temperature of 4 hours is changed into 500 respectively, 525,
550th, 575 and 600 DEG C of outer, remaining reaction condition and operation and CZS in embodiment 20.5- SCN-1 preparation method is identical,
Composite photo-catalyst CZS is prepared respectively0.5-SCN-500、CZS0.5-SCN-525、CZS0.5-SCN-550、CZS0.5-SCN-575、
CZS0.5-SCN-600。
Prepare catalyst D1, its preparation method and CZS0.5The difference of-SCN-550 composite photo-catalysts is：Save step
(1) first from room temperature to 500 DEG C of calcining 0.5h process in, directly " sandwich " layer structure is put into Muffle furnace,
Under nitrogen protection, with 5 DEG C/min heating rates from room temperature to 4h is calcined after 550 DEG C, it is cooled to after room temperature, product is ground
Powder is milled to, D1 catalyst is produced.
Choose CZS0.5-SCN-500、CZS0.5-SCN-550、CZS0.5- SCN-600 is scanned through Electronic Speculum sign, such as Fig. 5 institutes
Show, during low temperature calcination, because calcining heat is relatively low, the gas that thiocarbamide discharges in polycondensation process is less, SCN crystallinity
Poor, the SCN of generation is covered in CZS0.5Surface (Fig. 5 a)；As calcining heat is raised, the gas discharged in thiocarbamide polycondensation process
It is more, part CZS0.5Particulate load is on SCN surface (Fig. 5 b), and when calcining heat reaches 600 DEG C, thiocarbamide polycondensation produces a large amount of
Gas, generation SCN amounts are less, more CZS0.5Particulate load is on SCN surfaces (Fig. 5 c).
Embodiment 4：The zinc source composite photo-catalyst photocatalytic degradation rhodamine B (RhB) different with cadmium source mol ratio and first
Nitre is rattled away azoles (MTZ)
To investigate composite photo-catalyst CZS prepared by different mol ratio zinc source and cadmium sourcex1-SCN-x2Photocatalytic activity,
The sample prepared using embodiment 1 carries out photocatalytic degradation RhB and MTZ experiment.
A:The 1x10 for taking 50mL to be prepared with distilled water-5Mol/L RhB solution is put into 50mL light reactions bottle, totally 10 parts, then
Composite photo-catalyst sample, the SCN of the preparation of embodiment 2 prepared by 50mg embodiments 1 are added into bottle respectively, being stirred overnight makes it
Reach adsorption equilibrium.With 350W xenon lamp (upper sea blue bright, lambda1-wavelength is more than 420nm) irradiation light reaction bulb 45 minutes.With
Ultraviolet-visible spectrophotometer (Shimadzu UV-2450) detects its absorbance at 551nm.By the decolouring for comparing each sample
Rate carrys out the photocatalytic activity (such as table 2) of quantitatively characterizing sample.Its calculating formula is：Percent of decolourization=(ε0-ε)/ε0, ε0It is respectively with ε
Absorbance after RhB initial absorbance and reaction 45min.
B:The 50mg/L MTZ solution for taking 50mL to be prepared with distilled water is put into 50mL light reactions bottle, totally 10 parts, then distinguish
SCN prepared by composite photo-catalyst sample, embodiment 2 prepared by 10mg experimental examples 1 is added into bottle, ultrasonic disperse is after 2 minutes,
Magnetic agitation reaches adsorption equilibrium in 30 minutes.With 350W xenon lamp (upper sea blue bright, lambda1-wavelength is more than 420nm) irradiation
Light reaction bottle 60 minutes.Its absorbance at 319nm is detected with ultraviolet-visible spectrophotometer (Shimadzu UV-2450).Pass through
Compare the photocatalytic activity (such as table 3) that observed rate constant carrys out quantitatively characterizing sample.
The zinc source of the table 2. composite photo-catalyst photocatalytic degradation RhB percent of decolourization different with cadmium source mol ratio
From Table 2, it can be seen that SCN, the different mol ratio example zinc source synthesized with this law and cadmium source composite photo-catalyst
CZSxThe percent of decolourization of-SCN-8 (wherein x be 0.1,0.2,0.3 ... 0.8,0.9) photocatalytic degradation rhodamine B is respectively 14.4%,
58.2%th, 70.7%, 57.1%, 76.6%, 86.0%, 58.3%, 35.8%, 78.9%, 77.1%, wherein CZS0.5-SCN-
8 show best catalytic activity.
The zinc source of the table 3. composite photo-catalyst photocatalytic degradation MTZ different with cadmium source mol ratio observed rate constant
As can be seen from Table 3 SCN, synthesized with this law different mol ratio example zinc source and cadmium source composite photo-catalyst
CZSxThe observed rate constant of-SCN-8 (wherein x is 0.1,0.2,0.3 ... 0.8,0.9) photocatalytic degradation antibiotic flagyl
Respectively 1.39 × 10-2、2.36×10-2、3.57×10-2、2.48×10-2、5.15×10-2、6.61×10-2、3.42×10-2、1.99×10-2、5.69×10-2With 5.21 × 10-2/min.The catalytic activity of composite photo-catalyst is apparently higher than one-component
Catalyst SCN, therefore, the composite photo-catalyst prepared by this law have good photocatalysis performance.
Embodiment 5：Sulfur doping g-C3N4The different composite photo-catalyst photocatalytic degradation rhodamine B (RhB) of content and phenol
To investigate different content sulfur doping g-C3N4Composite photo-catalyst photocatalytic activity, using in case study on implementation 2
Sample carries out the experiment of photocatalytic degradation RhB and phenol.
A:Take that 50mL is prepared with distilled water 1 × 10-5Mol/L RhB solution is put into light reaction bottle, totally 6 parts, then distinguish
Sample prepared by 50mg embodiments 2 is added into bottle, is stirred overnight and reaches adsorption equilibrium.It is (upper sea blue with 350W xenon lamp
Bright, incident wavelength is more than 420nm) irradiation light reaction bulb 45 minutes.Examined with ultraviolet-visible spectrophotometer (Shimadzu UV-2450)
Survey its absorbance at 551nm.Lived by comparing the percent of decolourization of each sample come the photocatalysis of quantitatively characterizing (such as table 4) each sample
Property.Its calculating formula is：Percent of decolourization=(ε0-ε)/ε0, ε0It is the absorbance after the initial of RhB and reaction 45min respectively with ε.
B:Take that 50mL is prepared with distilled water 1 × 10-4Mol/L phenol solutions are put into light reaction bottle, totally 6 parts, then distinguish
Sample prepared by 50mg embodiments 2 is added into bottle, is stirred overnight and reaches adsorption equilibrium.It is (upper sea blue with 350W xenon lamp
Bright, incident wavelength is more than 420nm) irradiation light reaction bulb 90 minutes.With high performance liquid chromatography (Dionex Ultimate 3000)
Detect its concentration.By comparing the observed rate constant of each sample come the photocatalytic activity of quantitatively characterizing (such as table 5) each sample.
The sulfur doping g-C of table 4.3N4The different composite photo-catalyst photocatalytic degradation RhB percent of decolourizations of content
| Sample | SCN | CZS0.5-SCN-1 | CZS0.5-SCN-2 | CZS0.5-SCN-4 | CZS0.5-SCN-5 | CZS0.5 |
| Percent of decolourization (%) | 14.4 | 55.2 | 99.5 | 41.0 | 31.3 | 6.4 |
From table 4, it can be seen that SCN, the sulfur doping g-C of the different content synthesized with this method3N4Composite photo-catalyst sample
Product, CZS0.5-SCN-1、CZS0.5-SCN-2、CZS0.5-SCN-4、CZS0.5- SCN-5 and CZS0.5Photocatalytic degradation RhB's is de-
Color rate is respectively 14.4%, 55.2%, 99.5%, 41.0%, 31.3% and 6.4%, wherein sample CZS0.5- SCN-2 decolouring
Rate reaches 99.5%, and catalytic activity is significantly higher than other catalyst.
The sulfur doping g-C of table 5.3N4The different composite photo-catalyst Photocatalytic Degradation of Phenol observed rate constant of content
As can be seen from Table 5, SCN, the sulfur doping g-C of the different content synthesized with this method3N4Composite photo-catalyst sample
Product, CZS0.5-SCN-1、CZS0.5-SCN-2、CZS0.5-SCN-4、CZS0.5- SCN-5 andCZS 0.5Photocatalytic Degradation of Phenol is apparent
Speed constant is respectively 0.79 × 10-2、2.68×10-2、4.51×10-2、1.53×10-2、1.01×10-2With 0.40 × 10-2/
Min, the catalytic activity of composite photo-catalyst is above one-component catalyst.
Embodiment 6：The composite photo-catalyst photocatalytic degradation rhodamine B (RhB) prepared under different calcining heats
To investigate the photocatalytic activity of the composite photo-catalyst prepared under the different calcining heats of the present invention, case study on implementation is utilized
The sample prepared in 3 carries out photocatalytic degradation RhB experiment.The 1x10 for taking 50mL to be prepared with distilled water-5Mol/L RhB solution is put
Enter in light reaction bottle, totally 6 parts, then add the sample of the preparation of 50mg embodiments 3 into bottle respectively, be stirred overnight and reach absorption
Balance.With 350W xenon lamp (upper sea blue bright, incident wavelength is more than 420nm) irradiation light reaction bulb 45 minutes.Use ultraviolet-visible
Spectrophotometer (Shimadzu UV-2450) detects its absorbance at 551nm.The photocatalytic activity of sample is by comparing each sample
Percent of decolourization carry out quantitatively characterizing (such as table 6).Its calculating formula is：Percent of decolourization=(ε0-ε)/ε0, ε0Be respectively with ε the initial of RhB and
React the absorbance after 45min.
As can be seen from Table 6, D1, the sample CZS synthesized with this method under different calcining heats0.5-SCN-500、
CZS0.5-SCN-525、CZS0.5-SCN-550、CZS0.5- SCN-575 and CZS0.5- SCN-600 photocatalytic degradations RhB percent of decolourization
Respectively 11.9%, 27.1%, 59.9%, 99.5%, 18.6%, 15.3%.Wherein, D1 catalytic activity is less than other and answered
Close catalyst, wherein sample CZS0.5- SCN-550 degradeds RhB percent of decolourization reaches 99.5%, and catalytic activity is significantly higher than other
Catalyst.Composite photo-catalyst photocatalytic degradation RhB percent of decolourizations under the different calcining heats of table 6.
Claims (11)
1. a kind of composite photo-catalyst, it is characterised in that preparation method comprises the following steps successively：
（1）Prepare zinc-cadmium sulfide precursor powder；
（2）Take thiocarbamide to be placed in mortar after grinding, be divided into two parts, the thiocarbamide after a copy of it is ground is laid in crucible
In, then by step（1）In the zinc-cadmium sulfide precursor powder for preparing be laid in thiocarbamide surface, then after another is ground
Thiocarbamide be laid in zinc-cadmium sulfide precursor powder surface, form " sandwich " layer structure；
（3）Under nitrogen protection, by step（2）In " sandwich " layer structure first at 400~500 DEG C calcine 0.1~1 h
Afterwards, 500~600 DEG C are warming up to continue to calcine 0.5-4 h, is cooled to after room temperature, product is ground to powder, be combined
Photochemical catalyst.
2. composite photo-catalyst according to claim 1, it is characterised in that：The step（2）Middle zinc-cadmium sulfide presoma
The mass ratio of powder and thiocarbamide is 1-2:1-10.
3. composite photo-catalyst according to claim 1, it is characterised in that the preparation of the zinc-cadmium sulfide precursor powder
Method comprises the following steps：
（1）Inorganic zinc salt and inorganic cadmium salt are added in solvent, stirs, obtains homogeneous transparent mixed solution A；Meanwhile, another
Sulfurous organic compound is added in one container equipped with solvent, dispersed with stirring obtains homogeneous transparent solution B；
（2）By step（1）Middle gained mixed solution A and solution B mix to form mixed solution C, by mixed solution C ultrasound
After scattered 0.5~4 h, solvent is rotated out, powder is obtained；
（3）By step（2）Obtained powder, which is placed in mortar, to be ground, and obtains zinc-cadmium sulfide precursor powder.
4. composite photo-catalyst according to claim 3, it is characterised in that：Described inorganic zinc salt and inorganic cadmium salt rub
You are than being 1:0.1-9.
5. composite photo-catalyst according to claim 4, it is characterised in that：The inorganic zinc salt and inorganic cadmium salt addition
Summation and sulfurous organic compound mol ratio be 1:1~1:4.
6. composite photo-catalyst according to claim 5, it is characterised in that：Described inorganic zinc salt is zinc chloride, sulfuric acid
One or more in zinc, zinc nitrate and zinc acetate.
7. composite photo-catalyst according to claim 6, it is characterised in that：Described inorganic cadmium salt is caddy, sulfuric acid
One or more in cadmium, cadmium nitrate and cadmium acetate.
8. composite photo-catalyst according to claim 7, it is characterised in that：Described solvent is alcohols, acetone or water.
9. composite photo-catalyst according to claim 8, it is characterised in that：The sulfurous organic compound is thiocarbamide.
10. according to any described composite photo-catalyst in claim 1-9, it is characterised in that：The composite photo-catalyst contains
There are zinc-cadmium sulfide solid solution pellet and sulfur doping g-C3N4, and the load of zinc-cadmium sulfide solid solution pellet is dispersed in sulfur doping g-C3N4
Surface.
11. in a kind of claim 1-10 any described composite photo-catalyst photocatalytically degradating organic dye, antibiotic or
Application in aldehydes matter.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108246331A (en) * | 2018-01-16 | 2018-07-06 | 东北师范大学 | ZnS micro-composites of graphene carbonization nitrogen quantity point modification and its preparation method and application |
| CN109701584A (en) * | 2019-03-01 | 2019-05-03 | 华东交通大学 | A kind of Z-type light-catalyst ZnO/Fe2O3/g-C3N4Preparation method and application |
| CN110064346A (en) * | 2019-05-21 | 2019-07-30 | 华南理工大学 | A kind of titanium dioxide/zinc-cadmium sulfide graphene aerogel and the preparation method and application thereof |
| CN110280280A (en) * | 2019-07-31 | 2019-09-27 | 商丘师范学院 | Black phosphorus nanometer sheet, zinc sulphide/black phosphorus nanometer sheet preparation method and applications |
| CN113209997A (en) * | 2021-03-31 | 2021-08-06 | 南昌航空大学 | Near-infrared light response CuS/S-C3N4Preparation method of heterojunction nano composite material |
| CN116328791A (en) * | 2023-03-21 | 2023-06-27 | 中南大学 | Photocatalyst, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590413A (en) * | 2009-06-26 | 2009-12-02 | 天津工业大学 | Has visible light-responded Zinc-cadmium sulfide photocatalyst and preparation method thereof |
| CN101844795A (en) * | 2010-03-19 | 2010-09-29 | 中南民族大学 | Preparation method of spiauterite-type zinc sulfide nano-sphere with high photocatalytic activity |
| CN106669759A (en) * | 2016-12-26 | 2017-05-17 | 湖南大学 | Phosphor sulfur co-doped graphite phase carbon nitride photo-catalyst, preparation method and application thereof |
| CN105709836B (en) * | 2016-03-21 | 2019-01-22 | 武汉理工大学 | A kind of felted Zn that flexibility easily recycles1-xCdxS@PAN photochemical catalyst and preparation method thereof |
-
2017
- 2017-07-26 CN CN201710619407.6A patent/CN107262132B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590413A (en) * | 2009-06-26 | 2009-12-02 | 天津工业大学 | Has visible light-responded Zinc-cadmium sulfide photocatalyst and preparation method thereof |
| CN101844795A (en) * | 2010-03-19 | 2010-09-29 | 中南民族大学 | Preparation method of spiauterite-type zinc sulfide nano-sphere with high photocatalytic activity |
| CN105709836B (en) * | 2016-03-21 | 2019-01-22 | 武汉理工大学 | A kind of felted Zn that flexibility easily recycles1-xCdxS@PAN photochemical catalyst and preparation method thereof |
| CN106669759A (en) * | 2016-12-26 | 2017-05-17 | 湖南大学 | Phosphor sulfur co-doped graphite phase carbon nitride photo-catalyst, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| KELIN HEET.AL: ""Enhanced visible light photocatalytic H2 production over Z-scheme g-C3N4 nansheets/WO3 nanorods nanocomposites loaded with Ni(OH)x cocatalysts"", 《CHINESE JOURNAL OF CATALYSIS》 * |
| XIXI WANGET.AL: ""Enhanced efficiency and stability for visible light driven water splitting hydrogen production over Cd0.5Zn0.5S/g-C3N4 composite photocatalyst"", 《SCIENCEDIRECT》 * |
| 李覃: ""硫化物基光催化剂的制备和可见光光催化剂产氢活性"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108246331A (en) * | 2018-01-16 | 2018-07-06 | 东北师范大学 | ZnS micro-composites of graphene carbonization nitrogen quantity point modification and its preparation method and application |
| CN108246331B (en) * | 2018-01-16 | 2020-04-17 | 东北师范大学 | ZnS micron composite material modified by graphene nitrogen carbide quantum dots and preparation method and application thereof |
| CN109701584A (en) * | 2019-03-01 | 2019-05-03 | 华东交通大学 | A kind of Z-type light-catalyst ZnO/Fe2O3/g-C3N4Preparation method and application |
| CN110064346A (en) * | 2019-05-21 | 2019-07-30 | 华南理工大学 | A kind of titanium dioxide/zinc-cadmium sulfide graphene aerogel and the preparation method and application thereof |
| CN110280280A (en) * | 2019-07-31 | 2019-09-27 | 商丘师范学院 | Black phosphorus nanometer sheet, zinc sulphide/black phosphorus nanometer sheet preparation method and applications |
| CN110280280B (en) * | 2019-07-31 | 2022-01-28 | 商丘师范学院 | Black phosphorus nanosheet, and preparation method and application of zinc sulfide/black phosphorus nanosheet |
| CN113209997A (en) * | 2021-03-31 | 2021-08-06 | 南昌航空大学 | Near-infrared light response CuS/S-C3N4Preparation method of heterojunction nano composite material |
| CN116328791A (en) * | 2023-03-21 | 2023-06-27 | 中南大学 | Photocatalyst, and preparation method and application thereof |
| CN116328791B (en) * | 2023-03-21 | 2024-05-14 | 中南大学 | Photocatalyst, and preparation method and application thereof |
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