CN109603824A - A kind of preparation method and application of silver/zinc oxide composite material - Google Patents
A kind of preparation method and application of silver/zinc oxide composite material Download PDFInfo
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- CN109603824A CN109603824A CN201811639492.3A CN201811639492A CN109603824A CN 109603824 A CN109603824 A CN 109603824A CN 201811639492 A CN201811639492 A CN 201811639492A CN 109603824 A CN109603824 A CN 109603824A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 272
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 141
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 14
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 11
- 239000004246 zinc acetate Substances 0.000 claims abstract description 11
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims abstract description 10
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims abstract description 10
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 10
- 229960005261 aspartic acid Drugs 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 229960000314 zinc acetate Drugs 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 7
- 230000008859 change Effects 0.000 claims abstract description 6
- 229960001516 silver nitrate Drugs 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 25
- 238000007146 photocatalysis Methods 0.000 abstract description 19
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 16
- 229940012189 methyl orange Drugs 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 10
- 230000007246 mechanism Effects 0.000 abstract description 10
- 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 abstract description 9
- 229940043267 rhodamine b Drugs 0.000 abstract description 9
- 238000000862 absorption spectrum Methods 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000002441 X-ray diffraction Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 239000010944 silver (metal) Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 44
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 8
- -1 Ag/ZnO compound Chemical compound 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000006101 laboratory sample Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000644035 Clava Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002696 acid base indicator Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing 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
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (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
A kind of preparation method and application of silver/zinc oxide composite material is related to the preparation of Zinc oxide photochemical catalyst and applied technical field.After mixing by zinc acetate, silver nitrate, L-Aspartic acid, diethanol amine and deionized water, hydro-thermal reaction is carried out in reaction kettle, product is washed, is drying to obtain silver/zinc oxide composite material.It is promoted than zinc oxide much by the effect of the photocatalysis experiment discovery silver/zinc oxide composite material to methyl orange, rhodamine B.Utilize the test of scanning electron microscope, X-ray diffraction spectrogram, UV-visible absorption spectrum etc., and it is compared with the microstructure of zinc oxide, and ZnO, Ag/ZnO are analyzed from growth mechanism, photocatalytic mechanism, it was found that after Ag load, rodlike zinc oxide can preferably be assembled into rule body, change the distribution of charges of zinc oxide surface, it is empty to improve zinc oxide light induced electron.Generally speaking, the load of Ag has good effect for the promotion of the performance of zinc oxide.
Description
Technical field
The present invention relates to the preparation of Zinc oxide photochemical catalyst and applied technical fields, are specifically related to a kind of silver/zinc oxide
The preparation method and application of composite material.
Background technique
With the progress of society and science and technology, the development in terms of material is also constantly moving ahead.In the last century 80's, for
Nano material is made that and much studies and achieve good progress.Preparation and performance study in terms of film obtain very well
Achievement.1991, Japanese Scientists Iijimas observed carbon nanotube using Electronic Speculum for the first time, and on this basis, people are to receiving
Rice material has increasing interest.Z.K.Tang in 1997 et al.]ZnO film is had studied, and is made for the research of descendant
Contribution.2001, Hang et al. had studied zinc oxide nanowire.Hereafter, on the basis of forefathers study, descendant is constantly right
ZnO material carries out deeper research, and up to the present, ZnO and its composite material have become in material science not
The a part that can or lack.
ZnO after having loaded silver, i.e. Ag/ZnO compound, there is many effects, can not only decompose and cause damages to the mankind
Pollutant etc., various bacteriums, virus etc. can also be killed, therefore become extremely to have to the research and development of ZnO and its compound
Meaning.The ZnO for having loaded silver has stronger absorption to ultraviolet light, and the ultraviolet light within the scope of wavelength 280-400nm has not
Wrong shielding action.From the quantity of document of the related ZnO delivered it is found that in recent years, since ZnO has unique performance advantage,
As a hot topic in the whole world, the close attention of global scholars is caused.And the forbidden band of its exclusive 3.37eV is wide
Degree is also shown as great potential possessed by photochemical catalyst.The manufacturing conditions of ZnO are simple and clear, easily operated.ZnO light is urged
Agent has many advantages, and preparation cost is cheap, has preferable stability and biocompatibility, and the organic dirt degraded
It is more to contaminate species, not will cause too big pollution.
By physical method or chemical method with different Metal Supporteds on the surface ZnO to improve its photocatalysis performance, it is right
This, many scholars are made that unremitting trial.It is numerous studies have shown that can by ZnO area load noble metal (such as gold, silver,
Platinum, palladium, silver, iron etc.) or transition metal, improve ZnO photocatalysis performance.Ag/ZnO compound is research in numerous noble metals
One of hot spot, by consulting a large amount of documents in relation to Ag/ZnO, it has been found that during the preparation of Ag/ZnO compound, silver
Existing way in the reaction system is more with AgNO3, under the reduction of corresponding reducing agent, Ag+It is reduced to
Ag, Zn2+, ZnO then is generated under the action of mineralizer, is finally synthesizing Ag/ZnO compound.Due to this preparation method letter
Singly it is illustrated easy to be widely used by international community.It will be appreciated, however, that when synthesizing Ag/ZnO in this way, when
When being supported on the content raising of the Ag on ZnO, Ag nano particle diameter hardly results in effective control.
Summary of the invention
For the technical problems in the prior art, the present invention provides a kind of preparations of silver/zinc oxide composite material
Method.Meanwhile the present invention also provides a kind of applications of prepared silver/zinc oxide composite material.
To achieve the goals above, the technical scheme adopted by the invention is as follows: a kind of preparation of silver/zinc oxide composite material
Method after mixing by zinc acetate, silver nitrate, L-Aspartic acid, diethanol amine and deionized water carries out water in reaction kettle
Thermal response, product is washed, is drying to obtain silver/zinc oxide composite material.
As the optimal technical scheme of preparation method of the invention, zinc acetate, silver nitrate, L-Aspartic acid, diethanol amine
Additive amount ratio with deionized water is 1.8mmol-2.5mmol:0.15mmol-0.25mmol:100mg-120mg:10mL:5mL.
Hydrothermal temperature is 140 DEG C -160 DEG C, reaction time 12h-24h.Hydro-thermal reaction product is washed with deionized twice, connects
Washed twice again with dehydrated alcohol, then be dried.Sample drying temperature is 40 DEG C, drying time 12h.
In the prior art, zinc oxide has many good qualities and disadvantage in fields such as photocatalysis, and wherein degradation rate is lower, repeats benefit
It is low the disadvantage is that needing Improvement with rate.The present invention is on the basis of forefathers study, with the micron order ZnO of hydro-thermal method preparation
It is research object with Ag/ZnO compound, the shadow for studying Ag to ZnO by carrying out every characterization and photocatalysis experiment to it
It rings.
Compared with prior art, beneficial effects of the present invention are shown:
(1) rodlike zinc oxide is prepared with the raw materials hydro-thermal method such as zinc acetate, diethanol amine, L-Aspartic acid, deionized water, it is right
It is characterized, and as a result proves that micron order zinc oxide has photocatalysis performance, but effect is not good enough, and being gone out by sem analysis should
The zinc oxide structures that method is prepared are not regular enough, and particle is larger, and have fracture, incomplete phenomenon, lead to photocatalysis effect
Generally.
(2) silver nitrate hydro-thermal legal system equally is added with raw materials such as zinc acetate, diethanol amine, L-Aspartic acid, deionized waters
Standby Ag/ZnO compound.Find that its effect is promoted much than zinc oxide by the photocatalysis experiment to methyl orange, rhodamine B.
Using the test of scanning electron microscope, X-ray diffraction spectrogram, UV-visible absorption spectrum etc., and with the microstructure of zinc oxide into
Row comparison, and ZnO, Ag/ZnO are analyzed from growth mechanism, photocatalytic mechanism, discovery is after Ag load, rodlike zinc oxide energy
It is enough to be preferably assembled into rule body, change the distribution of charges of zinc oxide surface, it is empty to improve zinc oxide light induced electron.Generally speaking,
The load of Ag has good effect for the promotion of the performance of zinc oxide.
Detailed description of the invention
Fig. 1 is the XRD spectrum that embodiment 1 prepares Ag/ZnO sample 1.
Fig. 2 is pure ZnO, pure Ag and the X-ray diffractogram for preparing ZnO, Ag/ZnO sample.
Fig. 3 is the FESEM map that embodiment 1 prepares Ag/ZnO sample 1.
Fig. 4 is the FESEM figure for the Ag/ZnO sample being prepared under different condition.
Fig. 5 is the UV-visible absorption spectrum of the degradation methyl orange of Ag/ZnO sample 2.
Fig. 6 is the UV-visible absorption spectrum of photocatalysis laboratory sample.
Fig. 7 is the photocatalytic mechanism figure of Ag/ZnO.
Specific embodiment
Made with reference to embodiments with preparation method and application of the attached drawing to silver/zinc oxide composite material of the invention into
The detailed description of one step.
Embodiment 1
Scheme one: zinc acetate, L-Aspartic acid, diethanol amine and deionized water are first added sequentially to the reaction kettle of 25mL
In and uniformly mix, be subsequently placed in baking oven and react.Products obtained therefrom is washed with deionized twice after reaction, then again
It is washed twice with dehydrated alcohol, then puts it into vacuum oven drying 12 hours, temperature sets 40 DEG C, after drying to obtain the final product
ZnO powder.
Feed change component, hydrothermal temperature, time, and make four groups of samples.Data are shown in Table 1.
1 ZnO sample preparation each group raw material proportioning of table and reaction condition
| Sample number into spectrum | 1 | 2 | 3 | 4 |
| Zinc acetate (mmol) | 1.8 | 2.0 | 2.5 | 2.0 |
| L-Aspartic acid (mg) | 100 | 100 | 120 | 120 |
| Diethanol amine (ml) | 10 | 10 | 10 | 10 |
| Deionized water (ml) | 5 | 5 | 5 | 5 |
| Temperature (DEG C) | 140 | 140 | 140 | 140 |
| Time (h) | 12 | 12 | 12 | 12 |
Scheme two: zinc acetate, silver nitrate, L-Aspartic acid, diethanol amine and deionized water are first added sequentially to 25mL
Reaction kettle in and uniformly mix, be subsequently placed in baking oven and react.Products obtained therefrom is washed with deionized two after reaction
It is secondary, it is then washed twice again with dehydrated alcohol, then puts it into vacuum oven drying 12 hours, temperature sets 40 DEG C, does
Up to Ag/ZnO powder (under normal circumstances, the load capacity of Ag about 0%~10%) after dry.
Feed change component, hydrothermal temperature, time, and make four groups of samples.Data are shown in Table 2.
2 Ag/ZnO sample preparation each group raw material proportioning of table and reaction condition
Embodiment 1 prepares the Morphological Characterization of product:
1, X-ray diffractometer (XRD)
The characterizing method is the diffracted ray that is generated using X-ray to sample to obtain data, draws diffraction pattern by data
Its structure is composed and analyzed, the type etc. of various object phases can also be analyzed with this.
The present invention measures the diffraction data of sample using the sensible TD-3500X x ray diffractometer x in Dandong.Fig. 1 is embodiment 1
Prepare the XRD spectrum of Ag/ZnO sample 1.By analysis chart 1 it follows that 2 θ: 31.769 °, 34.421 °, 36.252 °,
47.538 °, 56.602 °, 62.862 °, 67.961 ° of corresponding diffraction crystal faces (100), (002), (101), (102),
(110), (103), (112) can be determined as ZnO (PDFNo.36-1451), show in product containing hexagonal wurtzite structure
ZnO, and 2 θ of dot mark are 38.116 °, 44.277 °, 64.426 ° and respectively correspond diffraction crystal face (111), (200), (220),
Analysis is the diffraction maximum (PDFNo.04-0783) of metallic silver, is determined in sample containing metal simple-substance silver.And it can be with from map
Find out that each peak position is all apparent, almost without miscellaneous peak, illustrates that the Ag/ZnO of preparation is purer.
Fig. 2 is pure ZnO, pure Ag and the X-ray diffractogram for preparing ZnO, Ag/ZnO sample, and a, b, c respectively represent ZnO in figure
Sample 1, Ag/ZnO sample 1, Ag/ZnO sample 2.The aforementioned diffraction maximum for having analyzed ZnO, and it is judged as it for hexagonal crystal system
Structure.Wherein in b, c curve, three diffraction maximums are had more compared with a, it is corresponding with (04-0783) card in PDF card, it analyzes
It is Ag phase.From figure 2 it can be seen that the diffraction maximum of ZnO does not change substantially, the load of Ag does not influence ZnO diffraction
Peak illustrates that Ag is only attached to the surface of ZnO, does not influence the internal structure of ZnO micron particles, and silver-colored from b, c
Diffraction maximum to can be seen that diffraction maximum silver-colored in Ag/ZnO sample 2 higher, it may be possible in Ag/ZnO sample 2 silver-colored load capacity compared with
Caused by height.
2, field emission scanning electron microscope (FESEM)
Scanning electron microscope is one of most direct means of current research material structure.It has lot of advantages: (1)
Feature image is clear；(2) high resolution；(3) image information is various informative etc..Sample is scanned using electronics is focused, and
Its surface is set to generate secondary electron, field scan coil plays the role of the power changed immediately to this beam electrons, so that electronics is swept
It retouches on some region of sample, and interact with sample, excitation generates physical signal.Distinguished with different detectors
It is monitored, amplify, is imaged, micro-analysis is carried out.Mainly secondary electron and the back scattering point that scanning electron microscope is collected
Son.
Sample is characterized using Hitachi JSM-5600 field emission scanning electron microscope in the present invention.Fig. 3 is to implement
Example 1 prepares the FESEM map of Ag/ZnO sample 1.As can be seen from Figure 3 the clava for possessing hexagonal structure is zinc oxide micrometer
Stick, some little particles of surrounding package are silver particles, and the surface of zinc oxide is attached in the form of simple substance.ZnO stick particle
Size is about 6 μm, wherein varying.
Fig. 4 is the FESEM figure for the Ag/ZnO sample being prepared under different condition, and comparison is as can be seen that Fig. 4 a from figure
In (Ag/ZnO sample 2) ZnO growth it is preferable, rodlike zinc oxide is assembled into flower-shaped, more regular, the circular granular of surrounding
For Ag particle, it can be seen that Ag particle is not attached to the surface ZnO well, relatively more mixed and disorderly.Compared to Fig. 4 a, from Fig. 4 b (Ag/
ZnO sample 3), in Fig. 4 c (Ag/ZnO sample 4) it can be seen that ZnO Rod-like shape is bigger, and have the phenomenon that fracture.Ag/
The load capacity of ZnO sample 2 is higher, so the additive amount of Ag may influence whether the growth of ZnO.Ag/ZnO sample 3, Ag/ZnO sample
The reaction time of product 4 is 12 hours, is reduced compared with 2 reaction time of Ag/ZnO sample, it is possible that being caused in appearance due to this
State situation.Meanwhile having incomplete flower-shaped ZnO structure in Fig. 4 b, this group of example reaction temperature is 140 DEG C, relative reduction reaction temperature
Degree reduces, and flower-like structure is caused to complete and (do not occur in Fig. 4 a, 4c) without growth well.
Embodiment 2
Photocatalysis experiment and UV-vis spectroscopy spectrum (uv-vis) analysis
Methyl orange (C14H14N3SO3Na), it can be used for acid-base indicator, shape is orange red powder, in alkalinity.Rhodamine
B(C28H31CIN2O3), it is a kind of organic dyestuff more difficult to degrade, is had centainly because it is with toxicity, and to food, water source
Pollution danger, pass through the performance to rhodamine B and the photocatalytic degradation experimental study sample of methyl orange so quasi-.
The ZnO sample or Ag/ZnO sample for weighing 40mg are mixed with the methyl orange of 10mL or rhodamine B solution, and are added
40mL deionized water is placed on magnetic stirring apparatus under light protected environment and stirs 60min, then with irradiating 60min under xenon lamp, when beginning
2mL is sampled with suction pipe, takes a sample every 10min.Then the absorption of UV-vis spectroscopy spectrometer measurement sample solution is utilized
For curve since the group in every kind of substance has any different to the absorption of ultraviolet light and visible light, structure difference causes extinction amount not
Together, therefore, qualitative and quantitative analysis is carried out to substance using the difference of the different absorbances of absorption curve.The present invention will use
The V-650 UV-vis spectroscopy spectrometer of Japanese Jasco company characterizes laboratory sample.
Fig. 5 is that Ag/ZnO sample 2 is degraded the UV-visible absorption spectrum of methyl orange, in Fig. 5 a, b, c be respectively 0min,
The methyl orange sample taken out when 20min, 40min.Fig. 6 is the UV-visible absorption spectrum of photocatalysis laboratory sample, in Fig. 6
A, b, c are that sample, Ag/ZnO sample 2 when ZnO sample 1 is added to methyl orange photocatalysis 20min are added to methyl orange light respectively
Sample when being catalyzed 20min, sample solution light absorption curve when Ag/ZnO sample 2 is added to rhodamine B photocatalysis 20min.
From figure 5 it can be seen that the absorption peak that methyl orange is located at 450nm gradually decreases, explanation with the growth of time
The concentration of methyl orange is reducing, although relatively slowly, it can be seen that Ag/ZnO is to have certain degradation capability to methyl orange
's.From fig. 6 it can be seen that the absorption peak ratio Ag/ZnO that ZnO is added to methyl orange photocatalysis 20min sample solution is added to first
Base orange light is catalyzed the absorption peak height of 20min sample, and with the time, the former absorbs peak height and illustrates its methyl orange concentration height, and degradation rate is not so good as
The latter, i.e. Ag/ZnO are better than ZnO to the photocatalysis effect of methyl orange.To confirm Ag mentioning to the photocatalysis performance of ZnO
Rise effect.Curve c can be seen that very high for the absorption peak of rhodamine B solution from Fig. 6, illustrate Ag/ZnO to rhodamine B
Photocatalysis performance is more limited, and illustrates that rhodamine B is a kind of substance more difficult to degrade.
Embodiment 3
Reaction mechanism and product photocatalytic mechanism
1, the growth mechanism of ZnO and Ag/ZnO
(1) in hydro-thermal method reaction, ZnO has following reaction:
Zn2++4OH-→Zn(OH)4 2- (1)
ZnO→ZnOX(1-X)V0, 0 ﹤ X ﹤ 1 (3)
Presoma of the zinc acetate as product zinc oxide, diethanol amine provide alkaline environment, promote Zn (OH)4 2-Formation,
Namely promote the generation of zinc oxide precursor.
(2) the former step reactions of the growth of Ag/ZnO as ibid saved, complete on this basis by the load of Ag:
Zn2++4OH-→Zn(OH)4 2- (1)
ZnO→ZnOX(1-X)V0, 0 ﹤ X ﹤ 1 (3)
Ag++2OH→Ag(OH)2 - (4)
Zn(OH)4 2-+2Ag(OH)2 -→Ag2O/ZnO+2H2O+4OH- (5)
Ag2O/ZnO→Ag/ZnOX(1-X)V0, 0 ﹤ X ﹤ 1 (6)
Its growth course and upper section are substantially similar.
2, Ag/ZnO photocatalytic mechanism
The photocatalysis effect of ZnO can be improved in the load of Ag, and Fig. 7 is the photocatalytic mechanism figure of Ag/ZnO, when Ag/ZnO by
To when illumination, especially ultraviolet lighting, the electrons on ZnO conduction band are moved on Ag, this reaction can make the light induced electron of ZnO
The efficiency separated with hole greatly improves, at this moment, O2、OH-It is reacted respectively with light induced electron, hole and generates O2 -With OH.It connects
Both groups participate in photocatalytic degradation reaction in, therefore, it can be seen that the photocatalysis efficiency of Ag/ZnO is than ZnO high
, while also demonstrating above-mentioned experiment.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (7)
1. a kind of preparation method of silver/zinc oxide composite material, which is characterized in that by zinc acetate, silver nitrate, L-Aspartic acid,
Diethanol amine and deionized water after mixing, carry out hydro-thermal reaction in reaction kettle, and product is washed, is drying to obtain silver/oxygen
Change zinc composite material.
2. preparation method as described in claim 1, which is characterized in that zinc acetate, silver nitrate, L-Aspartic acid, diethanol amine
Additive amount ratio with deionized water is 1.8mmol-2.5mmol:0.15mmol-0.25mmol:100mg-120mg:10mL:5mL.
3. preparation method as described in claim 1, which is characterized in that hydrothermal temperature is 140 DEG C -160 DEG C, the reaction time
For 12h-24h.
4. preparation method as described in claim 1, which is characterized in that hydro-thermal reaction product is washed with deionized twice, connects
Washed twice again with dehydrated alcohol, then be dried.
5. preparation method as described in claim 1 or 4, which is characterized in that sample drying temperature is 40 DEG C, and drying time is
12h。
6. a kind of silver/zinc oxide composite material prepared such as any one of claim 1-5 the method, which is characterized in that Ag
Son is carried on the surface of rodlike ZnO particle.
7. a kind of silver/zinc oxide composite material such as any one of claim 1-5 the method preparation is organic in photocatalytic degradation
Application in pollutant.
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| CN109728310A (en) * | 2019-01-11 | 2019-05-07 | 西南大学 | The preparation method of Ag/ZnO catalyst |
| CN110180540A (en) * | 2019-04-30 | 2019-08-30 | 苏州大学 | Ag dopen Nano metal oxide composite and its application in photocatalytic degradation tetracycline |
| CN110252299A (en) * | 2019-06-27 | 2019-09-20 | 太原理工大学 | A kind of ternary visible Ag/Ag2O/ZnO catalyst and its preparation method and application |
| CN111018365A (en) * | 2019-12-30 | 2020-04-17 | 黑龙江省科学院高技术研究院 | Method for in-situ preparation of silver nanoparticle loaded ZnO nano-foam |
| CN113060755A (en) * | 2021-03-09 | 2021-07-02 | 安徽景成新材料有限公司 | Preparation method of zinc oxide particles |
| CN113477250A (en) * | 2021-07-16 | 2021-10-08 | 新乡医学院 | Carbon fiber cloth @ porous ZnO two-dimensional nanosheet array @ Ag2Synthesis method of O nanoparticle ternary heterojunction |
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| CN110180540A (en) * | 2019-04-30 | 2019-08-30 | 苏州大学 | Ag dopen Nano metal oxide composite and its application in photocatalytic degradation tetracycline |
| CN110252299A (en) * | 2019-06-27 | 2019-09-20 | 太原理工大学 | A kind of ternary visible Ag/Ag2O/ZnO catalyst and its preparation method and application |
| CN111018365A (en) * | 2019-12-30 | 2020-04-17 | 黑龙江省科学院高技术研究院 | Method for in-situ preparation of silver nanoparticle loaded ZnO nano-foam |
| CN113060755A (en) * | 2021-03-09 | 2021-07-02 | 安徽景成新材料有限公司 | Preparation method of zinc oxide particles |
| CN113477250A (en) * | 2021-07-16 | 2021-10-08 | 新乡医学院 | Carbon fiber cloth @ porous ZnO two-dimensional nanosheet array @ Ag2Synthesis method of O nanoparticle ternary heterojunction |
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