CN109126800A - A kind of preparation method of cuprous oxide-copper-zine oxide composite photo-catalyst - Google Patents
A kind of preparation method of cuprous oxide-copper-zine oxide composite photo-catalyst Download PDFInfo
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- CN109126800A CN109126800A CN201810809229.8A CN201810809229A CN109126800A CN 109126800 A CN109126800 A CN 109126800A CN 201810809229 A CN201810809229 A CN 201810809229A CN 109126800 A CN109126800 A CN 109126800A
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- catalyst
- presoma
- cuprous oxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003751 zinc Chemical class 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 26
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 26
- 229940112669 cuprous oxide Drugs 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 4
- 229960005055 sodium ascorbate Drugs 0.000 claims description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 abstract description 7
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 6
- 238000001782 photodegradation Methods 0.000 abstract description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 29
- 239000010949 copper Substances 0.000 description 29
- 229910052802 copper Inorganic materials 0.000 description 24
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 23
- 239000011592 zinc chloride Substances 0.000 description 22
- 235000005074 zinc chloride Nutrition 0.000 description 22
- 239000011787 zinc oxide Substances 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of cuprous oxide-copper-zine oxide composite photo-catalyst preparation methods, and be related to Photodegradation catalyst preparation field, which is characterized in that the described method comprises the following steps: step 1 prepares presoma；Step 2, by presoma made from step 1, first cleaning repeatedly, then in ethanol solution is cleaned repeatedly in deionized water, then collects presoma drying；Presoma after step 2 drying is transferred in tube furnace by step 3, and set temperature is 200~600 DEG C, is passed through nitrogen, obtains cuprous oxide-copper-zine oxide composite photo-catalyst after being sintered 2-10h.The method of the present invention can be realized the pattern and cuprous oxide-copper-zine oxide ternary component ratio flexible modulation of composite photo-catalyst, regulate and control the pattern and component ratio of composite photo-catalyst by adjusting the ratio of the cupric salt and divalent zinc salt that initially add, and the ratio of three kinds of ingredients in composite catalyst can be regulated and controled under same pattern by changing washing times.
Description
Technical field
The present invention relates to Photodegradation catalyst preparation fields more particularly to a kind of cuprous oxide-copper-zine oxide complex light to urge
The preparation method of agent.
Background technique
Due to having photoproduction occurs under visible light for the P-type semiconductor that cuprous oxide is 2.2eV as a kind of forbidden bandwidth
The separation and nontoxic characteristic of electrons and holes, obtain in photolysis water hydrogen and Visible Light Induced Photocatalytic organic pollutant field
Important application.But light induced electron and hole are very easy to compound, reduce the catalytic activity of cuprous oxide.Preparation oxidation is sub-
Copper-based composite material is taken as a kind of effective mode to reduce the recombination rate of electron hole pair and light induced electron.
Zinc oxide semi-conductor is equally a kind of excellent catalysis material, has very high light sensitivity and chemical stability,
But wider forbidden bandwidth (3.5eV) makes zinc oxide be merely able to that electron hole separation occurs under ultraviolet excitation, can be ultraviolet
Accounting of the light within the scope of solar spectrum is again very small, and this greatly limits the applications of zinc oxide.Therefore substantially effectively sharp
With the huge challenge that sunlight is in zinc oxide photocatalysis material application.Currently, a variety of methods are used to zinc oxide
Absorption region expand to visible-range, including depositing noble metal particle, containing transition metal ion and compound other are partly led
Body etc., wherein the light abstraction width of zinc oxide can not only be expanded to visible-range with other semiconductors couplings, and
It can promote the separation in light induced electron and hole, to significantly improve photocatalysis efficiency.
Have benefited from the local surface plasma resonance effect of metal nanoparticle, plasma light catalyst has very high
Catalytic performance.In general, by the granular size of design metal, pattern and base dielectric matter, plasma light catalyst can be
Good photocatalysis effect is shown in full sunlight spectral region.Current research is primarily with regard to gold and silver nano-grain base
Plasma light catalyst, but noble metal gold and silver price be significantly higher than copper metal nano particle, cause gold and silver nanoparticle
The synthesis cost of the plasma light catalyst of particle base is very high.
Therefore, those skilled in the art is dedicated to developing a kind of system of cuprous oxide-copper-zine oxide composite photo-catalyst
Preparation Method not only allows composite photo-catalyst obtained to show good photocatalysis effect in full sunlight spectral region
Fruit, and simplify the preparation method of composite photo-catalyst in the prior art, significantly reduce the synthesis of composite photo-catalyst at
This.
Summary of the invention
In view of the above drawbacks of the prior art, technical problem to be solved by the invention is to provide a kind of cuprous oxide-
The preparation method of copper-zine oxide composite photo-catalyst allows composite photo-catalyst obtained in full sunlight spectral region
Good photocatalysis effect is inside shown, and simplifies the preparation method of photochemical catalyst in the prior art, is significantly reduced multiple
The synthesis cost of light combination catalyst.
To achieve the above object, the present invention provides a kind of cuprous oxide-copper-zine oxide composite photo-catalyst preparation sides
Method, which is characterized in that the described method comprises the following steps:
Step 1 prepares presoma, comprising:
Step 1.1, prepare precursor solution be at room temperature 1~4 according to molar ratio by mantoquita and zinc salt ratio model
It is stirred on blender after enclosing mixing；
Step 1.2, to step 1.1 mantoquita and zinc salt mixed solution in be added 4 times of mantoquita molal quantitys sodium hydroxide
Solution stirring；
Step 1.3, the sodium ascorbate solution that 5 times of mantoquita molal quantitys are added into the end reaction solution in step 1.2,
Presoma is made；
Step 2, by presoma made from step 1, first cleaning is multiple in deionized water, then cleaning is more in ethanol solution
It is secondary, then collect presoma drying；
Presoma after step 2 drying is transferred in tube furnace by step 3, and set temperature is 200-600 DEG C, is passed through nitrogen
Gas obtains final product cuprous oxide-copper-zine oxide composite photo-catalyst after being sintered 2-10h.
Further, in the step 2, wash number is respectively set to 3~9 in deionized water and in ethanol solution
It is secondary.
Further, the molar ratio of the mantoquita and the zinc salt is 1: 1~4: 1.
Further, the mantoquita is cupric salt soluble easily in water, and the zinc salt is divalent zinc salt soluble easily in water.
Further, in the step 1.1, the agitator speed is set as 100~1000r/min.
Further, in the step 1.2, mixing time is 1min or more.
Further, in the step 1.3, the reaction time is 30min~3h.
Further, in the step 2, setting presoma drying temperature is 50~100 DEG C, and drying time is 1h or more.
Cuprous oxide of the invention-copper-zine oxide composite photo-catalyst preparation method compared with prior art, advantage
It is:
(1) cuprous oxide made from the method for the present invention-copper-zine oxide composite photo-catalyst can be in full sunlight spectrum model
Good photocatalysis effect is shown in enclosing；
(2) the method for the present invention can be realized the three metamember ratio of pattern and cuprous oxide-copper-zine oxide of composite photo-catalyst
The flexible modulation of example, the shape of composite photo-catalyst is regulated and controled by adjusting the ratio of the cupric salt and divalent zinc salt that initially add
Looks and component ratio, and the ratio of three kinds of ingredients in composite catalyst can be regulated and controled under same pattern by changing washing times；
(3) the method for the present invention significantly reduces the cost for preparing composite photo-catalyst for nano particle base with gold and silver.
It is described further below with reference to technical effect of the attached drawing to design of the invention, specific structure and generation, with
It is fully understood from the purpose of the present invention, feature and effect.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of a preferred embodiment of the invention；
When Fig. 2 is that copper chloride and zinc chloride molar ratio are 4: 1 in the present invention, the XRD comparison diagram of presoma sintering front and back；
Fig. 3 (a) to Fig. 3 (d) is the SEM for the composite photo-catalyst that copper chloride and zinc chloride different ratio obtain in the present invention
Figure；
Fig. 4 is that copper chloride and zinc chloride different ratio obtain the XRD comparison diagram of composite photo-catalyst in the present invention；
When Fig. 5 is that copper chloride and zinc chloride molar ratio are 4: 1 in the present invention, different numbers are cleaned with water and ethyl alcohol and are answered
The XRD comparison diagram of light combination catalyst.
Specific embodiment
2 preferred embodiments of the invention are introduced below with reference to Figure of description, keep its technology contents more clear and just
In understanding.The present invention can be emerged from by many various forms of embodiments, and protection scope of the present invention not only limits
The embodiment that Yu Wenzhong is mentioned.
Embodiment 1
Such as Fig. 1, the present invention provides a kind of cuprous oxide-copper-zine oxide composite photo-catalyst preparation method flow charts
It is shown, comprising the following steps: step 1 prepares presoma；Step 2, by presoma made from step 1 first it is clear in deionized water
It washes 3~9 times, then is cleaned in ethanol solution 3~9 times, then collect presoma and dry 1h or more at 50~100 DEG C；Step
3, the presoma after step 2 drying is transferred in tube furnace, set temperature is 200-600 DEG C, is passed through nitrogen, is sintered 2-10h
After obtain final product cuprous oxide-copper-zine oxide composite photo-catalyst.Preparation method of the invention will use mantoquita and zinc
Salt, in an embodiment of the present invention, mantoquita are cupric salt soluble easily in water, and zinc salt is divalent zinc salt soluble easily in water, this hair
Bright middle cupric salt is copper chloride, and divalent zinc salt is zinc chloride.Wherein, it includes: in room that step 1, which prepares the specific steps of presoma,
It is stirred on blender after mixing the proportional region that copper chloride solution and liquor zinci chloridi are 1~4 according to molar ratio under temperature, if
Determining agitator speed is 100~1000r/min, and the hydroxide of 4 times of copper chloride molal quantitys is added into mixed solution while stirring
Sodium solution stirring 1 minute or more, the sodium ascorbate solution of 5 times of copper chloride molal quantitys is added into reaction solution, the reaction was continued
30mins-3h.When preparing forerunner's precursor reactant and starting, the molar ratio of copper chloride solution and liquor zinci chloridi is set as 1: 1,4: 3,
2: 1 and 4: 1, this proportion can guarantee that obtained presoma has preferable dispersibility and homogeneity.It is prepared in the present invention
In the reaction system of method, on the one hand bivalent cupric ion can be reduced into cuprous oxide by sodium ascorbate, on the other hand can be with
Ascorbic acid zinc complex is formed with divalent zinc ion.
Embodiment 2
The present invention provides a kind of cuprous oxide-copper-zine oxide composite photo-catalyst preparation methods, including following step
Rapid: then copper chloride and liquor zinci chloridi are added in aqueous solution according to the ratio that molar ratio is 4: 1 by mixed solution step 1
It is placed on blender, setting speed is that 100-1000r/min starts to stir, and 4 times of chlorine are added into mixed solution while stirring
Change the sodium hydroxide solution of copper molal quantity, stirring 1 minute or more, the anti-bad of 5 times of copper chloride molal quantitys is added into reaction solution
Hematic acid sodium solution, the reaction was continued 30mins-3h.Presoma made from step 1 is first cleaned 3~9 by step 2 in deionized water
It is secondary, then cleaned in ethanol solution 3~9 times, it then collects presoma and dries 1h or more at 50~100 DEG C；Step 3 will walk
Presoma after rapid 2 drying is transferred in tube furnace, and set temperature is 200-600 DEG C, is passed through nitrogen, is obtained after being sintered 2-10h
Final product cuprous oxide-copper-zine oxide composite photo-catalyst.
Such as Fig. 2, in a preferred embodiment of the invention, when copper chloride and zinc chloride molar ratio are 4: 1, forerunner obtained
Shown in the XRD comparison diagram of body sintering front and back, the XRD diagram before sintering is shown, is near 30 °, 36 °, 42 °, 61 °, 73 ° in the angle of diffraction
There is the diffraction maximum of cuprous oxide, there is no the diffraction maximum of copper and zinc oxide, sintered XRD diagram is shown, in the angle of diffraction
Nearby there is the diffraction maximum of cuprous oxide for 30 °, 36 °, 42 °, 61 °, 73 °, is 43 ° and 50 ° in the angle of diffraction and nearby occurs
The diffraction maximum of copper is to occur zinc oxide faint diffraction maximum near 32 ° and 56 ° in the angle of diffraction.High temperature sintering is in the present invention
In it is most important, sintering can convert zinc oxide for the ascorbic acid zinc complex for being attached to cuprous oxide surface.Meanwhile
Under high temperature, ascorbic acid zinc complex can reduction-oxidation it is cuprous.By sintering, cuprous oxide-can be converted by presoma
Copper-zine oxide composite photo-catalyst.It is compared with the traditional method, the present invention prepares zinc oxide and copper by once sintered, grasps
Make simple and effective, whole process does not use any surfactant, cuprous oxide-copper-zine oxide composite photocatalyst of acquisition
Agent clean surface, photocatalytic activity with higher.
Such as Fig. 3 (a) to Fig. 3 (d), in a preferred embodiment of the invention, copper chloride and zinc chloride different ratio are obtained
Composite photo-catalyst SEM figure shown in, when not adding zinc chloride, shown in the pattern of presoma obtained such as Fig. 3 (a), shape
Like cube；When the molar ratio of copper chloride and zinc chloride is 4: 1, shown in the pattern of presoma obtained such as Fig. 3 (b)；Work as chlorine
When the molar ratio of change copper and zinc chloride is 2: 1, shown in the pattern of presoma obtained such as Fig. 3 (c)；When copper chloride and zinc chloride
When molar ratio is 1: 1, shown in the pattern of presoma obtained such as Fig. 3 (d).By Fig. 3 (b) to Fig. 3 (d) it is found that when copper chloride with
The ratio of zinc chloride from 4: 1 be reduced to 1: 1 when, the pattern of presoma obtained gradually changes into sea urchin shape from cubic.
1 copper chloride of table and zinc chloride different ratio obtain the molar ratio of copper and Zn-ef ficiency in the EDS map of presoma
| Cu2+∶Zn2+ | 4∶1 | 2∶1 | 1∶1 |
| Cu element: Zn element | 3.98 | 2.23 | 1.42 |
Table copper chloride and zinc chloride different ratio as above obtain mole of copper and Zn-ef ficiency in the EDS map of presoma
Than shown, the relative amount of zinc chloride is improved, so that the relative amount of Zn-ef ficiency gradually increases in presoma obtained, thus chlorine
After changing the presoma sintering that copper and zinc chloride different ratio obtain, in obtained cuprous oxide-copper-zine oxide composite photo-catalyst
Zn-ef ficiency content also gradually increases.
Such as Fig. 4, in a preferred embodiment of the invention, composite photocatalyst that copper chloride and zinc chloride different ratio obtain
The XRD comparison diagram of agent it is found that when the molar ratio of copper chloride and zinc chloride is 1: 1,2: 1 and 4: 1, the angle of diffraction be 43 °,
50 °, 74 ° nearby there is the diffraction maximum of copper, are 30 °, 36 °, 42 °, 61 °, 73 ° in the angle of diffraction and cuprous oxide nearby occur
Diffraction maximum is 32 °, 34 °, 56 °, 62.5 °, 67.5 ° in the angle of diffraction and nearby the diffraction maximum of zinc oxide occurs, this shows the present invention
Cuprous oxide, copper, zinc oxide are crystalline state in cuprous oxide made from method-copper-zine oxide composite photo-catalyst, with chlorination
Copper and zinc chloride, which are matched from 1: 1, increases to 4: 1, and diffraction peak intensity of the copper near 43 ° successively successively decreases.Correspondingly, cuprous oxide
It compares with the content of zinc oxide and also changes.
(111) of cuprous oxide are brilliant in the composite photo-catalyst XRD spectrum that 2 copper chloride of table and zinc chloride different ratio obtain
(111) crystal face peak intensity ration statistics of face peak intensity and copper
| Cu2+∶Zn2+ | 4∶1 | 2∶1 | 1∶1 |
| Cu2O(111)∶Cu(111)(XRD peak value ratio) | 1.67 | 0.83 | 0.55 |
Cuprous oxide in the composite photo-catalyst XRD spectrum that table copper chloride and zinc chloride different ratio as above obtain
(111) (111) crystal face peak intensity ration statistics figure of crystal face peak intensity and copper is it is found that the amount for increasing zinc salt can improve complex light and urge
The relative amount of copper in agent.Therefore, the final of products therefrom can be regulated and controled by regulating and controlling initial mantoquita and zinc salt ratio
Ingredient.In practical applications, it is required according to specific, the ratio of flexible modulation mantoquita and zinc salt can be obtained with optimality
The composite photo-catalyst of energy.The pattern and ingredient of composite photo-catalyst influence the catalytic performance of composite photo-catalyst very big.This
While the advantage of invention is that granule-morphology can be regulated and controled, the ultimate constituent to composite photo-catalyst can also be realized
It control effectively.
Such as Fig. 5, when copper chloride and zinc chloride molar ratio are 4: 1 in the present invention, different numbers are cleaned with water and ethyl alcohol and are obtained
Composite photo-catalyst XRD comparison diagram shown in because wash number will affect the ingredient of finally obtained composite photo-catalyst
Ratio.When precursor water and ethyl alcohol respectively wash 3 times, it is 43 °, 50 °, 74 ° in the angle of diffraction and spreading out for copper atom nearby occurs
Penetrate peak, the angle of diffraction be 30 °, 36 °, 61 ° nearby there is the diffraction maximum of cuprous oxide, the angle of diffraction be 32 °, 34 °, 56 °,
62.5 °, 67.5 ° nearby there is the diffraction maximum of zinc oxide；When precursor deionized water and ethyl alcohol respectively wash 9 times, spreading out
Firing angle is 43 °, 50 °, 74 ° and nearby the diffraction maximum of copper atom occurs, and it is sub- oxidation occur near the angle of diffraction is 30 ° and 61 °
The diffraction maximum of copper is 32 ° and 34 ° in the angle of diffraction and the diffraction maximum of zinc oxide, spreading out near 56 °, 62.5 °, 67.5 ° nearby occurs
Penetrating peak becomes very faint.
The deionized water of table 3 and ethyl alcohol clean different numbers and obtain cuprous oxide in the XRD comparison diagram of composite photo-catalyst
(111) crystal face peak intensity and copper (111) crystal face peak intensity ratio
| Wash number | 3 | 9 |
| Cu2O(111)∶Cu(111)(XRD peak value ratio) | 0.45 | 0.5 |
Table deionized water as above and ethyl alcohol clean different numbers and obtain aoxidizing Asia in the XRD comparison diagram of composite photo-catalyst
Shown in (111) crystal face peak intensity of copper and (111) crystal face peak intensity ratio of copper, when increasing to 9 times by 3 times with washing times,
(111) crystal face peak intensity of cuprous oxide and (111) crystal face peak intensity ratio of copper increase to 0.5 from 0.45.It is sub- to be attached to oxidation
The ascorbic acid zinc complex on copper surface is reduced, and the content of the zinc oxide and copper that obtain after sintering is reduced.Therefore, presoma is controlled
Washing pass can regulate and control cuprous oxide in final product, the relative amount of three kinds of ingredients of zinc oxide and copper.In practical application
In, it can also change presoma after the ratio for determining initial mantoquita and zinc salt according to specific catalysis reactant and go
Washing times in ionized water and ethyl alcohol are finely adjusted the ultimate constituent of composite photo-catalyst, obtain the optimal photocatalysis of performance
Agent.The present invention is not under conditions of changing granule-morphology, by simply changing the mode of washing to presoma, can be realized pair
The ingredient of catalyst granules is finely adjusted, to increase the approach of regulation particulate component.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that this field ordinary skill which
It according to the present invention can conceive without creative work and make many modifications and variations.Therefore, all skills in the art
Art personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (9)
1. a kind of cuprous oxide-copper-zine oxide composite photo-catalyst preparation method, which is characterized in that the method includes with
Lower step:
Step 1 prepares presoma, comprising:
Step 1.1 prepares precursor solution at room temperature to mix mantoquita and zinc salt according to the proportional region that molar ratio is 1~4
It is stirred on blender after conjunction；
Step 1.2, to step 1.1 mantoquita and zinc salt mixed solution in be added 4 times of mantoquita molal quantitys sodium hydroxide solution
Stirring；
Step 1.3, the sodium ascorbate solution that 5 times of mantoquita molal quantitys are added into the end reaction solution in step 1.2, are made
Presoma；
Step 2, by presoma made from step 1, first cleaning repeatedly, then in ethanol solution is cleaned repeatedly, so in deionized water
Presoma drying is collected afterwards；
Presoma after step 2 drying is transferred in tube furnace by step 3, and set temperature is 200-600 DEG C, is passed through nitrogen, is burnt
Final product cuprous oxide-copper-zine oxide composite photo-catalyst is obtained after knot 2-10h.
2. cuprous oxide as described in claim 1-copper-zine oxide composite photo-catalyst preparation method, which is characterized in that excellent
Choosing, in the step 2, wash number is respectively set to 3~9 times in deionized water and in ethanol solution.
3. cuprous oxide as described in claim 1-copper-zine oxide composite photo-catalyst preparation method, which is characterized in that institute
The molar ratio for stating mantoquita and the zinc salt is 1: 1~4: 1.
4. cuprous oxide as described in claim 1-copper-zine oxide composite photo-catalyst preparation method, which is characterized in that institute
Stating mantoquita is cupric salt soluble easily in water, and the zinc salt is divalent zinc salt soluble easily in water.
5. cuprous oxide as described in claim 1-copper-zine oxide composite photo-catalyst preparation method, which is characterized in that institute
It states in step 1.1, sets the agitator speed as 100~1000r/min.
6. cuprous oxide as described in claim 1-copper-zine oxide composite photo-catalyst preparation method, which is characterized in that institute
It states in step 1.2, mixing time is 1min or more.
7. cuprous oxide as described in claim 1-copper-zine oxide composite photo-catalyst preparation method, which is characterized in that institute
It states in step 1.3, the reaction time is 30mins~3h.
8. cuprous oxide as described in claim 1-copper-zine oxide composite photo-catalyst preparation method, which is characterized in that step
In rapid 2, setting presoma drying temperature is 50~100 DEG C, and drying time is 1h or more.
9. cuprous oxide as claimed in claim-copper-zine oxide composite photo-catalyst preparation method, which is characterized in that step
In rapid 2, sintering temperature when preparing catalyst is 200-600 DEG C, need to be passed through inert nitrogen gas.
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