CN110102322A - The preparation method of flower-shaped Ag@AgBr/ZnO catalysis material - Google Patents
The preparation method of flower-shaped Ag@AgBr/ZnO catalysis material Download PDFInfo
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- CN110102322A CN110102322A CN201910519670.7A CN201910519670A CN110102322A CN 110102322 A CN110102322 A CN 110102322A CN 201910519670 A CN201910519670 A CN 201910519670A CN 110102322 A CN110102322 A CN 110102322A
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims description 33
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 238000007146 photocatalysis Methods 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims 1
- 241001614291 Anoplistes Species 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 25
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 20
- 238000006731 degradation reaction Methods 0.000 description 20
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 18
- 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 11
- 229940043267 rhodamine b Drugs 0.000 description 11
- 239000011941 photocatalyst Substances 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002073 nanorod Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- URDOHUPGIOGTKV-JTBFTWTJSA-M Cefuroxime sodium Chemical compound [Na+].N([C@@H]1C(N2C(=C(COC(N)=O)CS[C@@H]21)C([O-])=O)=O)C(=O)\C(=N/OC)C1=CC=CO1 URDOHUPGIOGTKV-JTBFTWTJSA-M 0.000 description 3
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- 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 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229960000534 cefuroxime sodium Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical compound [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 description 1
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 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
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- -1 Methylene Chemical group 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- AEEAZFQPYUMBPY-UHFFFAOYSA-N [I].[W] Chemical compound [I].[W] AEEAZFQPYUMBPY-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 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
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B01J35/39—
-
- B01J35/40—
Abstract
The invention discloses a kind of preparation methods of flower-shaped Ag@AgBr/ZnO catalysis material, belong to field of nano material preparation.This method uses following steps: 1) certain density surfactant and the source Zn is configured, as the source Zn solution；Certain density hexa and the source Ag are configured, as the source Ag solution；2) oxidant is added into the source Ag solution, and is added dropwise in the solution of the source Zn with given pace；3) mixed solution is transferred to autoclave, hydro-thermal reaction is carried out under certain time with certain temperature；4) product is calcined in air after washing alcohol washes drying, flower-shaped Ag@AgBr/ZnO catalysis material is obtained after being cooled to room temperature.The synthetic method process that the present invention uses is simple, easy to operate, without secondary pollution.The catalysis material of synthesis has the characteristics that pattern is uniform, has excellent performance.Present invention work belongs to field of photocatalytic material.
Description
Technical field
The present invention relates to the preparation methods of flower-shaped Ag@AgBr/ZnO catalysis material.
Background technique
ZnO is a kind of semiconductor catalyst for being widely used in photocatalysis oxidation technique, it possesses excellent photocatalysis
Active, stable chemical property and higher quantum yield, thus ZnO have in directions such as sewage treatments it is higher using valence
Value.However ZnO is a kind of semiconductor material with wide forbidden band, is only capable of by ultraviolet excitation photocatalysis oxidation reaction, to the benefit of sunlight
Only have 4% with rate, and ZnO, as catalysis material, there is also the fast problems of electron-hole pair recombination rate.These defects
Limit its practical application.In order to solve these defects of ZnO, people have carried out a series of trial.The study found that Ag@
AgBr plasma catalyst, since AgBr decomposes the plasma resonance effect of the Ag nanoparticle generated, Ag@in system
AgBr can carry out Photocatalytic Oxidation with responding to visible light, but due to its lesser intrinsic band gap, be directly used in photocatalysis
Oxidation, the effect is unsatisfactory.There is respective and deficiency in view of single catalyst, we answer Ag AgBr and ZnO
It closes, forms composite catalyst Ag@AgBr/ZnO, photochemical catalyst is greatly improved to the utilization rate of light, and can be in component
Between generate electronics transfer, delay the compound of electron-hole pair, improve the speed and efficiency of photocatalytic degradation of organic matter.In ring
Today of border situation very severe, researching and developing efficient composite photocatalyst is extremely urgent, existing theory significance, and has reality
Border value.
Lei Shi in 2013 et al. is in article " Highly efficient visible light-drivenAg/AgBr/
ZnO composite photocatalyst for degrading Rhodamine B " it is middle using deposition-precipitation two-step method
AgBr/ZnO catalysis material is obtained, then rodlike Ag/AgBr/ZnO nanocomposite is prepared by photoreduction met hod.It is simulating too
In the case that sunlight irradiates 1h, this sample of 0.05g is 94.7% to the degradation rate of the rhodamine B of 10mg/L.Two step of deposition-precipitation
The problems such as this preparation method of method combination photoreduction met hod, there are complicated for operation, process is cumbersome, long preparation period.
Qi Zhang in 2014 et al. is in article " In situ oxidation ofAg/ZnO by bromine water
To prepare ternary Ag-AgBr/ZnO sunlight-derived photocatalyst " in use bromine water situ oxygen
The Ag/ZnO microballoon for changing one kettle way preparation, obtains spherical Ag-AgBr/ZnO composite photocatalyst material.3h is irradiated in 300W iodine-tungsten lamp
In the case where, this sample of 0.1g is to the degradation rate of the rhodamine B of 5mg/L close to 100%.This preparation method removes preparation process
Cumbersome, except long preparation period, there is also the lower problems of spherical Ag-AgBr/ZnO degradation efficiency.
2011 Nian Xuyuan states et al. are in meeting " preparation of Ag/AgBr ZnO photocatalyst and its research of degradation methyl orange "
It is middle that Ag/AgBr@ZnO photocatalyst is prepared using hydro-thermal method.Illumination 3h is about 95% to the degradation rate of methyl orange.It is not difficult to find out that
Up to the degradation time of 3h, the efficiently quick advantage of photocatalytic oxidation can not be embodied.
2018 Nian Chengzhi rocs et al. are in patent " preparation method of porous Ag/AgBr nano material " (CN108975383A)
Porous Ag/AgBr material is prepared using hydro-thermal method.Ag/AgCl/AgBr presoma is prepared first in method, through ammonia
Ag/AgBr is obtained after aqueous solution washing removal AgCl, preparation process is not pointing directly toward the nano material finally prepared, to original
Material has certain waste.
Furnishings cloud in 2016 et al. is in patent " a kind of preparation and its application of photochemical catalyst Ag/AgBr "
(CN106111166A) using imidazolium ionic liquid 1- butyl -3- methylimidazole bromide ([BMIM] Br) as bromine source and forerunner in
Ag/AgBr photochemical catalyst is prepared in body hydro-thermal., it is worthwhile to note that ionic liquid can be strong absorb in air moisture (even if
It is hydrophobic ionic liquid), substantially reduce its performance；And in actual experiment, ionic liquid price is high, and purity is low (restricted
Standby process limits), it once being mixed with impurity, also will affect its performance, limit its actual application power.
2015 Nian Wangyong are strong et al. in patent " preparation method of the porous complex microsphere of visible light catalyst AgBr/Ag "
(CN104815679A) it is template that CuBr microballoon is used in, and preparing the porous complex microsphere of AgBr/Ag using ion-exchange can
Light-exposed catalyst.Degradation under plus the irradiation of the optical filter xenon lamp (500W) of 400nm, to the methyl orange of the 10mg/mL of 30mL
Rate reaches 90% or more.
Song Caixia in 2018 et al. is in patent " a kind of preparation method of Ag/ZnO nanometer rods self-assembly "
(CN108745354A) Ag/ZnO nanometer rods self-assembly presoma is prepared using spray drying process in, then is fired to obtain Ag/
ZnO nanorod hierarchical structure self-assembly.The Ag/ZnO nano-rod assembly catalysis material of preparation is used for photochemical catalyzing
Hydrogen manufacturing yield can be up to 1.07mmol/g-1h-1。
Zhao Jingzhong in 2018 et al. is in patent " a method of prepare Ag loading ZnO nanometer stick array "
(CN108970612A) in, ZnO seed layer substrate is prepared first, next prepares ZnO nano-rod array film, will finally be prepared into
Ag load is carried out to ZnO nano-rod array film, obtains Ag loading ZnO material.
Cai Fanpeng in 2017 et al. uses gas phase in patent " a kind of preparation method of hollow ZnO " (CN108002425A)
Spray heating decomposition in method prepares ZnO catalysis material.It is noted that the hollow ZnO material that this method is prepared
Fragmentation is serious, partial size is uneven, pattern disunity.It is active uncontrollable that this result will directly result in material light catalysis.
2018 Nian Xing man of virtue and ability armies et al. are in patent " preparation method of the micro-nano ZnO of morphology controllable under the conditions of a kind of atmospheric low-temperature "
(CN108275713A) the micro-nano ZnO of different morphologies is prepared under the conditions of atmospheric low-temperature.It is worth noting that this system
Preparation Method has used this solvent of oleyl amine, it is well known that oleyl amine has penetrating odor, can skin be burnt and be corroded.
The safety in production of this preparation method needs to be investigated.
Although the above method is made that contribution outstanding in terms of preparing catalysis material, these preparation methods are deposited
The problem of many general character, such as: preparation process is cumbersome, ingredient requirement is harsh and the obtained catalytic performance of special appearance catalyst not
By force.In comparison, the present invention uses one step hydro thermal method simple process, easy to operate, each parameter are easy to control, raw material is inexpensive
It is easy to get, the special appearance of catalyst is beneficial to the promotion of catalytic activity.And CTAB is in addition to controlling pattern as surfactant
Outside, bromine source is also acted as, pattern is controlled, saves raw material, is killed two birds with one stone.
In conclusion having synthesized the excellent flower-shaped Ag@of photocatalysis performance by simple one step hydro thermal method in the present invention
AgBr/ZnO material meets the related request in practical application to material.
Summary of the invention
The purpose of the present invention is to solve raw material valences existing for the preparation method of existing Ag@AgBr/ZnO catalysis material
Lattice are expensive, process flow it is complicated it is cumbersome, preparation time is long, production efficiency is not suitable for mass production and photochemical catalyst photocatalysis
The problems such as activity is poor provides a kind of preparation method of flower-shaped Ag@AgBr/ZnO catalysis material.
The preparation method of flower-shaped Ag@AgBr/ZnO catalysis material follows the steps below:
One, it is certain value by the ratio between amount of substance of Zn element, Ag element, hexa and surfactant, matches
The certain density source Zn and surfactant are set in 30mL distilled water, obtains the source Zn solution；Configure the certain density source Ag and
Oxidant is added in 20mL distilled water in hexa, obtains the source Ag solution；
Two, the source Ag solution is added dropwise in the solution of the source Zn with certain drop rate, mixed solution is shifted supreme
Reaction kettle is pressed to carry out hydro-thermal reaction, mixed solution accounts for about the 50% of reactor volume, maintains centainly with certain hydrothermal temperature
The hydro-thermal time.
Three, by product after washing, alcohol are washed and dried, Muffle furnace is moved into, is calcined under air atmosphere with certain temperature
Regular hour obtains the Ag@AgBr/ZnO catalysis material of floriform appearance after being cooled to room temperature.
The ratio between Zn element, Ag element, hexa and amount of substance of surfactant described in step 1 are
1:(0.01~0.4): 1:(0.1~1).
The source Zn described in step 1, surfactant, the source Ag and hexa concentration be respectively
0.3333mol/L, (0.03333~0.3333) mol/L, (0.05~0.2) mol/L and 0.5mol/L.
The source Zn described in step 1 is zinc sulfate (ZnSO4), Zinc diacetate dihydrate (C4H6O4Zn·2H2O), six hydration nitre
Sour zinc (Zn (NO3)2·6H2) or Zinc vitriol (ZnSO O4·7H2O) compound.
Surfactant described in step 1 is cetyl trimethylammonium bromide (CTAB)
Oxidant described in step 1 is H2O2(30%).
Drop rate described in step 2 is 1~3 second/drop；The hydrothermal temperature set is 100~180 DEG C；The hydro-thermal time
1~5 hour.
Calcination temperature described in step 3 is 500~800 DEG C；Calcination time is 1~3h.
Beneficial effects of the present invention are as follows:
The present invention as silver-colored source, makes material composition reach molecular level mixing using zinc salt and silver nitrate, synthesis by more
The flower-shaped Ag@AgBr/ZnO catalysis material chemical constituent of hole lamella composition is uniform；The present invention is using CTAB as surface-active
Agent can be effectively controlled the pattern and partial size of catalyst, and the flower-shaped Ag@AgBr/ZnO catalysis material for obtaining synthesis has unified
Pattern and uniform partial size；Meanwhile CTAB is also used as the source Br to participate in reaction, and without additionally selecting other sources Br, save the cost,
The preparation difficulty for effectively reducing Ag@AgBr/ZnO photochemical catalyst, the flower-shaped Ag@AgBr/ZnO being made of porous chips prepared
With extremely strong photocatalytic activity, meet the related request in practical application to material.
Detailed description of the invention
The SEM photograph of Fig. 1, the flower-shaped Ag@AgBr/ZnO material prepared using the method for the present invention
The XRD spectra of Fig. 2, the flower-shaped Ag@AgBr/ZnO material prepared using the method for the present invention
Fig. 3, the flower-shaped Ag@AgBr/ZnO material (specific embodiment one) prepared using the method for the present invention are to rhodamine B
Degradation efficiency and the photocatalysis time relation curve, catalytic amount 1gL-1, rhodamine B concentration 5mgL-1.In figure (a)
The degradation efficiency of rhodamine B when Ag@AgBr/ZnO material (specific embodiment one) is catalyzed under simulated solar irradiation；(b) do not make
With Ag@AgBr/ZnO material be catalyzed when under simulated solar irradiation rhodamine B natural degradation efficiency；(c) Ag@AgBr/ZnO material
The degradation efficiency of rhodamine B when (specific embodiment one) is catalyzed under no light condition.
Fig. 4, using flower-shaped Ag@AgBr/ZnO material (specific embodiment one) methylene blue of the method for the present invention preparation
The relation curve of degradation efficiency and photocatalysis time, catalytic amount 1gL-1, methylene blue concentration 10mgL-1。
Fig. 5, flower-shaped Ag@AgBr/ZnO material (specific embodiment one) Cefuroxime Sodium prepared using the method for the present invention
Degradation efficiency and the photocatalysis time relation curve, catalytic amount 1gL-1, cefuroxime na concn 20mgL-1。
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: the preparation method of Ag@AgBr/ZnO material light catalysis material flower-shaped in present embodiment
It follows the steps below:
One, it is 1:0.2:1 by the ratio between amount of substance of Zn element, Ag element, hexa and surfactant:
0.55 ratio weighs acetic acid dihydrate zinc, silver nitrate, hexa and CTAB, configuration 0.3333mol/L and
The source Zn of 0.1833mol/L and surfactant obtain the source Zn solution in 30mL distilled water；Configure 0.1mol/L and
Oxidant is added in 20mL distilled water in the source Ag of 0.5mol/L and hexa, the source Ag solution；
Two, the source Ag solution is added dropwise in the solution of the source Zn with the drop rate of 1 second/drop, mixed solution is transferred to
Autoclave carries out hydro-thermal reaction, and mixed solution accounts for about the 50% of reactor volume, the hydrothermal temperature set as 140 DEG C, and
It maintains the hydro-thermal time 3 hours at such a temperature；
Three, by product after washing, alcohol are washed and dried, Muffle furnace is moved into, with 650 DEG C of temperature calcinations under air atmosphere
2h obtains flower-shaped Ag@AgBr/ZnO catalysis material after being cooled to room temperature.
Present embodiment has the beneficial effect that: the flower-shaped Ag@AgBr/ZnO material of present embodiment synthesis has by more
The flower-like structure of hole lamella cluster composition, the direction of growth and cluster mode of photocatalyst crystals can be efficiently controlled using CTAB,
Its pattern is presented are as follows: being assembled into flower-shaped, flower-shaped Ag AgBr/ZnO material diameter by porous sheet cluster is about 4-6 μm,
As shown in Figure 1.Biggish size is conducive to the transfer of the free electron in photochemical catalyst photocatalytic process, and the result (Fig. 2) of XRD is aobvious
The highly crystalline property of composite material prepared by the present invention is shown, this characteristic is equally beneficial in photochemical catalyst photocatalytic process
Free electron transfer.The high efficiency of transmission of free electron can reduce the recombination probability of electron hole to a certain extent, make Ag@
AgBr/ZnO composite photocatalyst material embodies extremely excellent photocatalytic activity.
With the flower-shaped Ag@AgBr/ZnO material 1gL of preparation-1Degrade 5mgL-1Rhodamine B solution, simulated solar irradiation
Lower stirring 30min, degradation rate reach 99.11%.
With the flower-shaped Ag@AgBr/ZnO material 1gL of preparation-1Degrade 10mgL-1Methylene blue solution, simulated solar
30min is stirred under light, degradation rate reaches 99.99%.
With the flower-shaped Ag@AgBr/ZnO material 1gL of preparation-1Degrade 20mgL-1Cefuroxime sodium solution, simulation too
30min, degradation rate 74.77% are stirred under sunlight；150min is stirred, degradation rate reaches 95.09%.
Specific embodiment 2:
One, it is 1:0.2:1 by the ratio between amount of substance of Zn element, Ag element, hexa and surfactant:
0.55 ratio weighs acetic acid dihydrate zinc, silver nitrate, hexa and CTAB, configuration 0.3333mol/L and
The source Zn of 0.1833mol/L and surfactant obtain the source Zn solution in 30mL distilled water；Configure 0.1mol/L and
Oxidant is added in 20mL distilled water in the source Ag of 0.5mol/L and hexa, the source Ag solution；
Two, the source Ag solution is added dropwise in the solution of the source Zn with the drop rate of 3 seconds/drop, mixed solution is transferred to
Autoclave carries out hydro-thermal reaction, and mixed solution accounts for about the 50% of reactor volume, the hydrothermal temperature set as 160 DEG C, and
It maintains the hydro-thermal time 2.5 hours at such a temperature；
Three, by product after washing, alcohol are washed and dried, Muffle furnace is moved into, with 500 DEG C of temperature calcinations under air atmosphere
2.5h obtains flower-shaped Ag@AgBr/ZnO catalysis material after being cooled to room temperature.
Specific embodiment 3:
One, it is 1:0.2:1 by the ratio between amount of substance of Zn element, Ag element, hexa and surfactant:
0.55 ratio weighs acetic acid dihydrate zinc, silver nitrate, hexa and CTAB, configuration 0.3333mol/L and
The source Zn of 0.1833mol/L and surfactant obtain the source Zn solution in 30mL distilled water；Configure 0.1mol/L and
Oxidant is added in 20mL distilled water in the source Ag of 0.5mol/L and hexa, the source Ag solution；
Two, the source Ag solution is added dropwise in the solution of the source Zn with the drop rate of 2 seconds/drop, mixed solution is transferred to
Autoclave carries out hydro-thermal reaction, and mixed solution accounts for about the 50% of reactor volume, the hydrothermal temperature set as 130 DEG C, and
It maintains the hydro-thermal time 4 hours at such a temperature；
Three, by product after washing, alcohol are washed and dried, Muffle furnace is moved into, with 700 DEG C of temperature calcinations under air atmosphere
3h obtains flower-shaped Ag@AgBr/ZnO catalysis material after being cooled to room temperature.
Flower-shaped Ag AgBr/ZnO powder shown in the present invention can be used for photocatalysis Decomposition organic pollutant, with sunlight or
Ultraviolet light is light source.It when light-catalyzed reaction, carries out under agitation, a certain amount of catalyst (0.5~1g/L) is added, certain
In time (0.5~3h), organic dirt such as rhodamine B, methylene blue and Cefuroxime Sodium of degradation a certain concentration (5~20mg/L)
Contaminate the aqueous solution of object.Such as: catalytic degradation 5mg/L rhodamine B solution takes 100ml rhodamine B solution, and catalyst (0.5 is added
~1g/L), catalysis reaction is carried out under sunlight or ultraviolet light, at regular intervals (7.5~30min), 3~5ml of sampling is molten
After filtering, the variation of solution concentration is detected with the absorbance of ultraviolet-visible spectrophotometer measurement solution for liquid sample, thus
Calculate the degradation rate of organic pollutant.
Claims (8)
1. the preparation method of flower-shaped Ag@AgBr/ZnO catalysis material, it is characterised in that flower-shaped Ag@AgBr/ZnO photocatalysis
The preparation method of material follows the steps below:
It one, is certain value, configuration one by the ratio between amount of substance of Zn element, Ag element, hexa and surfactant
The source Zn for determining concentration and surfactant obtain the source Zn solution in 30mL distilled water；Configure the certain density source Ag and six Asias
Oxidant is added in 20mL distilled water in tetramine, the source Ag solution；
Two, the source Ag solution is added dropwise in the solution of the source Zn with certain drop rate, it is anti-that mixed solution is transferred to high pressure
Kettle is answered to carry out hydro-thermal reaction, mixed solution accounts for about the 50% of reactor volume, maintains certain hydro-thermal with certain hydrothermal temperature
Time.
Three, by product after washing, alcohol are washed and dried, Muffle furnace is moved into, it is certain with certain temperature calcining under air atmosphere
Time, the Ag@AgBr/ZnO catalysis material of floriform appearance is obtained after being cooled to room temperature.
2. the preparation method of the Ag@AgBr/ZnO catalysis material of floriform appearance according to claim 1, it is characterised in that step
The ratio between amount of substance of Zn element, Ag element, hexa and surfactant described in rapid one be 1:(0.01~
0.4): 1:(0.1~1).
3. the preparation method of the Ag@AgBr/ZnO catalysis material of floriform appearance according to claim 1, it is characterised in that step
The source Zn described in rapid one, surfactant, the source Ag and hexa concentration be respectively 0.3333mol/L,
(0.03333~0.3333) mol/L, (0.05~0.2) mol/L and 0.5mol/L.
4. the preparation method of the Ag@AgBr/ZnO catalysis material of floriform appearance according to claim 1, it is characterised in that step
The source Zn described in rapid one is zinc sulfate (ZnSO4), Zinc diacetate dihydrate (C4H6O4Zn·2H2O), zinc nitrate hexahydrate (Zn
(NO3)2·6H2) or Zinc vitriol (ZnSO O4·7H2O) compound.
5. the preparation method of the Ag@AgBr/ZnO catalysis material of floriform appearance according to claim 1, it is characterised in that step
Surfactant described in rapid one refers to cetyl trimethylammonium bromide (CTAB).
6. the preparation method of the Ag@AgBr/ZnO catalysis material of floriform appearance according to claim 1, it is characterised in that step
Oxidant described in rapid one is H2O2(30%).
7. the preparation method of the Ag@AgBr/ZnO catalysis material of floriform appearance according to claim 1, it is characterised in that step
Drop rate described in rapid two is 1~3 second/drop；The hydrothermal temperature set is 100~180 DEG C；The hydro-thermal time 1~5 hour.
8. the preparation method of the Ag@AgBr/ZnO catalysis material of floriform appearance according to claim 1, it is characterised in that step
Calcination temperature described in rapid three is 500~800 DEG C；Calcination time is 1~3h.
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