CN102962049A - Method for preparing nanometer photocatalytic material via hydrothermal reaction - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 9
- 230000001699 photocatalysis Effects 0.000 title abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011941 photocatalyst Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 27
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 abstract description 31
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000013032 photocatalytic reaction Methods 0.000 abstract 1
- 150000005837 radical ions Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 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
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Abstract
The invention discloses a method for preparing nanometer photocatalytic material via a hydrothermal reaction. The method comprises the steps of mixing water soluble sodium germanate and water soluble zinc salt according to a mole ratio of Zn to G2 of 2:1, magnetically stirring the mixed solution at the room temperature for 30-60 minutes, carrying out hydrothermal treatment at a temperature of 80-200 DEG C for 3-8 hours, and centrifuging and drying the reacted solution. The method has the marked characteristics as follows: through using the zinc salt with different acid radical ions, the draw ratio of a zinc germanate nanorod can be regulated and controlled; the water solution of the used sodium germanate has strong alkalinity, so that the prepared material can be used as a photocatalyst or an acidic-alkali corrosion resisting coating material in a photocatalytic reaction.
Description
Technical field
The present invention relates to a kind of acid-alkali-corrosive-resisting catalysis material the preparation method and in the application of photocatalysis field, particularly relate to a kind of hydrothermal synthesis method with catalysis material of nanorod structure.
Background technology
Photocatalysis technology is to have important application aspect the recyclable fuel at the photocatalysis depollution of environment, photocatalysis Decomposition aquatic products hydrogen and photocatalytic conversion carbon dioxide.Zn
2GeO
4As important catalysis material, because have organic pollutant degradation, water decomposition and photocatalysis CO
2The reduction ability and receive much concern.Catalysis material wants to obtain extensive use, and simple synthesis technique and stable chemical property must be arranged.Common Zn
2GeO
4Preparation technology be high temperature (greater than 1000C) solid phase reaction, this technique is very power consumption not only, and the Zn for preparing
2GeO
4Be polycrystalline material, its acid-alkali-corrosive-resisting is relatively poor, thereby has limited its application under strong acid or highly basic condition.Generally, compare with polycrystalline material, chemical stability is not better because do not have crystal boundary for monocrystal material.Therefore, for improving Zn
2GeO
4The chemical stability of material is expanded its range of application, need to overcome the prior art problem, and development cost is cheap, the simple Zn of technique
2GeO
4The preparation method of monocrystalline.
Summary of the invention
The object of the invention provides a kind of with low cost, simple synthetic method of technique and prepares the good Zn of chemical stability
2GeO
4The monocrystalline catalysis material is effectively to expand Zn
2GeO
4The range of application of catalysis material.
For solving the problems of the technologies described above, technical solution of the present invention is: hydro-thermal reaction prepares the method for nano-photocatalyst material, the invention provides a kind of hydro-thermal ion-exchange reactions method, prepares the good Zn of chemical stability
2GeO
4Monocrystal nano rod, prepared Zn
2GeO
4Monocrystal nano rod has represented good acid-alkali-corrosive-resisting.
Preparation process comprises: with water miscible sodium germanate and water miscible zinc salt according to the Zn:Ge=2:1 mixed in molar ratio; With mixed solution behind room temperature magnetic agitation 30-60min, at 80-200 ℃ of hydrothermal treatment consists 3-8h; With reacted solution centrifugal, drying.
Zinc salt is zinc sulfate, zinc nitrate, zinc acetate or zinc chloride.The reaction equation of described ion-exchange is Na
2GeO
3+ 2Zn
2+(X)
m+ H
2O=Zn
2GeO
4+ mH
- nX+mNa
nX, wherein, X can be SO
4 2-, NO
3 -, CH
3COO
-Or Cl
-, and when X be SO
4 2-The time, m=1, n=2; When X is NO
3 -, CH
3COO
-, Cl
-The time m=2, n=1.
Described sodium germanate solution is strong base solution.
The reaction of described ion-exchange is when X is SO
4 2-, NO
3 -, Cl
-The time, this ion-exchange reactions belongs to highly basic and prepares the strong acid reaction, when X is CH
3COO
-The time, this ion-exchange reactions is that highly basic prepares the weak acid reaction.
The microstructure of described germanic acid Zinc material is nanometer rods, and the draw ratio of nanometer rods can be regulated in the 2-50 scope.
The present invention also provides the chemical stability evaluation of above-mentioned germanic acid zinc monocrystal nano rod, and prepared germanic acid zinc nanometer rods does not all change pattern and composition in 120-220 ℃ of hydro-thermal and pH in the 0-14 scope, demonstrated extremely strong acid-alkali-corrosive-resisting.
The present invention also provides the purposes of germanic acid zinc nanometer monocrystalline bar material, namely in light-catalyzed reaction as photochemical catalyst.Prepared germanic acid zinc monocrystal nano rod catalysis material is applicable to the reduction of photocatalysis degradation organic contaminant, water-splitting and carbon dioxide.Prepared germanic acid zinc monocrystal nano rod also can be used as the coating material of acid-alkali-corrosive-resisting and uses.
Beneficial effect of the present invention is: provide a kind of with low cost, simple synthetic method of technique to prepare the good Zn of chemical stability
2GeO
4The monocrystalline catalysis material is effectively to expand Zn
2GeO
4The range of application of catalysis material.The notable feature of this synthetic method is: contain the zinc salt of different acid ions by employing, can realize the draw ratio of germanic acid zinc nanometer rods; The aqueous solution of the sodium germanate that adopts has strong basicity, and is different according to the zinc salt that adopts, and can form corresponding acid in the hydro-thermal reaction product, and therefore reaction belongs to highly basic relieving haperacidity reaction; Prepared germanic acid zinc nanometer rods has good chemical stability under the 120-220C hydrothermal condition, in the pH=0-14 scope.Prepared material can be used as photochemical catalyst and uses in light-catalyzed reaction, also can be used as the acid-alkali-corrosive-resisting coating material and uses.
Description of drawings
Fig. 1 is germanic acid zinc monocrystal nano rod hydro-thermal reaction preparation flow figure; Wherein, A) raw material Na
2GeO
3Particle; B) in deionized water, by disperseing Na
2GeO
3Powder obtains Na
2GeO
3Colloidal solid; C) add zinc ion, under hydrothermal condition, Na
2GeO
3Generate Zn with zinc ion generation ion-exchange reactions
2GeO
4Monocrystal nano rod.
Fig. 2 is Zn
2GeO
4Monocrystal nano rod and
pZn after H=0 or the 14 Water Under heat treatments
2GeO
4The XRD collection of illustrative plates of monocrystal nano rod;
Fig. 3 is with Zn (CH
3COO)
2Zn for the raw material preparation
2GeO
4The SEM figure (a) of monocrystal nano rod, TEM schemes (b), SEAD (c) and high-resolution TEM figure (d);
Fig. 4 is respectively with ZnCl
2(a), Zn (NO
3)
2(b) and ZnSO
4Zn for the raw material preparation
2GeO
4The SEM figure of monocrystal nano rod;
Fig. 5 is respectively with ZnCl
2(a), Zn (NO
3)
2(b) and ZnSO
4Zn for the raw material preparation
2GeO
4The ultraviolet-visible absorption curves of monocrystal nano rod;
Fig. 6 is respectively with ZnCl
2(a), Zn (NO
3)
2(b) and ZnSO
4Zn for the raw material preparation
2GeO
4The photo catalytic reduction CO of monocrystal nano rod
2Produce CH
4Performance comparison figure.
The specific embodiment
The present invention is further detailed explanation below in conjunction with accompanying drawing and the specific embodiment:
Experimental technique, feature: the crystalline phase of following preparing product is used CuK α radiation (λ=0.154178nm) determined by X-ray diffraction (XRD) (Ultima III of science, Japan) at 40kV and 40mA.20-80 ° sweep limits with 5 ° of min
-1Sweep speed at room temperature obtain the XRD collection of illustrative plates.The form of powder is detected by field emission scanning electron microscope (FESEM, FEI NOVA NANOSEM 230).The TriStar 3000 types specific surface that specific surface area size is produced by U.S. Micromeritics company-pore-size distribution analysis-e/or determining, N
2The adsorption/desorption of gas is finished under the 77K temperature, calculates its specific area with the BET method.Transmission electron microscope (TEM) photo and high-resolution-ration transmission electric-lens (HR-TEM) photo obtain with the JEM-3010 type transmission electron microscope of Japanese JEOL company, and operating voltage is 200kV.The ultraviolet-visible reflectance spectrum is obtained by the UV-2500PC type ultraviolet-visible spectrophotometer analysis that Japanese Shimadzu company produces, and converts absorption spectrum to by the Kubelka-Munk method.
Sample: all chemicals are AG, open the i.e. usefulness of bag, without being further purified.
Taking by weighing sodium germanate powder 0.166g is dissolved in the 15mL deionized water and (can prepares the sodium germanate powder by solid phase reaction, technology has had more report now), taking by weighing the 0.439g zinc acetate is dissolved in the 15mL deionized water, then the sodium germanate of 15mL is poured in the 15mL zinc acetate solution, with mixed solution behind room temperature magnetic agitation reaction 0.5h, in the 40mL water heating kettle of packing into, and 200 ℃ of hydrothermal treatment consists 3h(150 ℃ hydrothermal treatment consists 4h also can), naturally cool to room temperature, centrifugal, the dry rear Zn that obtains
2GeO
4Catalysis material.The X-ray powder diffraction result shows that the gained sample is the Zn of pure phase
2GeO
4(Fig. 2).The SEM image shows (Fig. 3 a), gained Zn
2GeO
4Sample has nanorod structure, and length is about 400nm, and diameter is about 100nm, the about 4:1 of draw ratio.TEM image (Fig. 3 b), choose electronic diffraction (Fig. 3 c) and high-resolution lattice image (Fig. 3 d) the analysis showed that prepared Zn
2GeO
4Sample is monocrystal nano rod.
Embodiment 2
Taking by weighing sodium germanate powder 0.166g is dissolved in the 15mL deionized water, taking by weighing the 0.544g zinc chloride is dissolved in the 15mL deionized water, then the sodium germanate of 15mL is poured in the 15mL liquor zinci chloridi, with mixed solution behind room temperature magnetic agitation reaction 0.5h, pack in the 40mL water heating kettle, and at 180 ℃ of hydrothermal treatment consists 5h, naturally cool to room temperature, centrifugal, the dry rear Zn that obtains
2GeO
4Catalysis material.The SEM image shows (Fig. 4 a), gained Zn
2GeO
4Sample has nanorod structure, and length is about 500nm, and diameter is about 50nm, the about 10:1 of draw ratio.The ultraviolet-visible spectrophotometer analysis shows that prepared samples band-gap is 4.66eV(Fig. 5).
Embodiment 3
Taking by weighing sodium germanate powder 0.166g is dissolved in the 15mL deionized water, taking by weighing the 0.594g zinc nitrate hexahydrate is dissolved in the 15mL deionized water, then the sodium germanate of 15mL is poured in the 15mL zinc nitrate solution, with mixed solution behind room temperature magnetic agitation reaction 0.5h, pack in the 40mL water heating kettle, and at 120 ℃ of hydrothermal treatment consists 8h, naturally cool to room temperature, centrifugal, the dry rear Zn that obtains
2GeO
4Catalysis material.The SEM image shows (Fig. 4 b), gained Zn
2GeO
4Sample has nanorod structure, and length is about 2000nm, and diameter is about 50nm, the about 40:1 of draw ratio.The ultraviolet-visible spectrophotometer analysis shows that prepared samples band-gap is 4.66eV(Fig. 5).
Taking by weighing sodium germanate powder 0.166g is dissolved in the 15mL deionized water, taking by weighing the 0.574g Zinc vitriol is dissolved in the 15mL deionized water, then the sodium germanate of 15mL is poured in the 15mL zinc nitrate solution, with mixed solution behind room temperature magnetic agitation reaction 0.5h, pack in the 40mL water heating kettle, and at 200 ℃ of hydrothermal treatment consists 5h, naturally cool to room temperature, centrifugal, the dry rear Zn that obtains
2GeO
4Catalysis material.The SEM image shows (Fig. 4 c), gained Zn
2GeO
4Sample has nanorod structure, and length is about 2000nm, and diameter is about 1000nm, the about 2:1 of draw ratio.The ultraviolet-visible spectrophotometer analysis shows that prepared samples band-gap is 4.54eV(Fig. 5).
Taking by weighing sodium germanate powder 0.332g is dissolved in the 15mL deionized water, taking by weighing the 1.088g zinc chloride is dissolved in the 15mL deionized water, then the sodium germanate of 15mL is poured in the 15mL liquor zinci chloridi, with mixed solution behind room temperature magnetic agitation reaction 0.5h, pack in the 40mL water heating kettle, and at 200 ℃ of hydrothermal treatment consists 5h, naturally cool to room temperature, centrifugal, the dry rear Zn that obtains
2GeO
4Catalysis material.Sem analysis shows, gained Zn
2GeO
4Sample has nanorod structure, and length is about 500nm, and diameter is about 50nm, the about 10:1 of draw ratio.
Embodiment 6
Take by weighing sodium germanate powder 0.1g Zn
2GeO
4Monocrystal nano rod (preparation method such as example 2) catalysis material, be dispersed in the NaOH aqueous solution of 30mL pH=14 or in the sulfuric acid solution of pH=0, pack in the 40mL water heating kettle, and at 200 ℃ of hydrothermal treatment consists 5h, naturally cool to room temperature, after centrifugal, the drying, XRD(Fig. 2) analyze to show still be the Zn of pure phase
2GeO
4, SEM observes to show still be nanorod structure.
Embodiment 7
With 0.1g Zn
2GeO
4It is 4.2cm that the monocrystal nano rod catalysis material is dispersed in area
2Glass reactor on, with the xenon lamp of 300W as light source, the about 230mL of the volume of whole reaction system.Before reaction, the air in the reaction unit is extracted out fully, import the pressure of high-purity Ar gas control reative cell processed, after repeating so to process several times, with high-purity CO
2It is constant pressure that gas passes into and make the pressure of reaction unit.The 0.4mL deionized water is injected in the reaction system as reducing agent, the half-light saturated adsorption was turned on light after several hours, during the light-catalyzed reaction, every certain interval of time is got about 0.5mL from reative cell gas inject assay products in the gas chromatograph (GC-2014, Japanese Shimadzu company).
Fig. 6 is respectively with ZnCl
2(a), Zn (NO
3)
2(b) and ZnSO
4Zn for the raw material preparation
2GeO
4The photo catalytic reduction CO of monocrystal nano rod
2Produce CH
4Performance comparison figure.As seen from the figure, with ZnCl
2Zn for the raw material preparation
2GeO
4Monocrystal nano rod has the highest photo catalytic reduction CO
2Performance, sem analysis shows, with ZnCl
2Zn for the raw material preparation
2GeO
4Monocrystal nano rod has maximum draw ratio, with ZnCl
2, Zn (NO
3)
2And ZnSO
4Zn for the raw material preparation
2GeO
4The specific area of monocrystal nano rod is respectively 48.4,38.6 and 21.8m
2/ g.As seen, with ZnCl
2Zn for the raw material preparation
2GeO
4Monocrystal nano rod has larger specific area, thereby has higher photocatalytic activity.
By above embodiment, the application has demonstrated with Na in the mode that exemplifies
2GeO
3Be raw material with different zinc salts, by the hydro-thermal reaction legal system standby the Zn of different draw ratios
2GeO
4Monocrystal nano rod, prepared Zn
2GeO
4Monocrystal nano rod has good acid-alkali-corrosive-resisting and high photocatalytic activity.But those of ordinary skills should be able to understand: the application's content required for protection is not limited to above-described embodiment, and the application's scope required for protection is shown in the application's claims.Those of ordinary skills can change experiment condition and feature on this basis, and obtain technical scheme required for protection in the application's claims scope, but this does not exceed scope of the present invention.
Claims (7)
1. hydro-thermal reaction prepares the method for nano-photocatalyst material, it is characterized in that step comprises: with water miscible sodium germanate and water miscible zinc salt according to the Zn:Ge=2:1 mixed in molar ratio; With mixed solution behind room temperature magnetic agitation 30-60min, at 80-200 ℃ of hydrothermal treatment consists 3-8h; With reacted solution centrifugal, drying.
2. method according to claim 1 is characterized in that, the reaction equation of described ion-exchange is Na
2GeO
3+ 2Zn
2+(X)
m+ H
2O=Zn
2GeO
4+ mH
- nX+mNa
nX, wherein, X is SO
4 2-, NO
3 -, CH
3COO
-Or Cl
-, and when X be SO
4 2-The time, m=1, n=2; When X is NO
3 -, CH
3COO
-, Cl
-The time m=2, n=1.
3. method according to claim 1 is characterized in that, described sodium germanate solution is strong base solution.
4. method according to claim 2 is characterized in that, the reaction of described ion-exchange is when X is SO
4 2-, NO
3 -, Cl
-The time, this ion-exchange reactions belongs to highly basic and prepares the strong acid reaction, when X is CH
3COO
-The time, this ion-exchange reactions is that highly basic prepares the weak acid reaction.
5. method according to claim 1, the microstructure that it is characterized in that described germanic acid Zinc material is nanometer rods, and the draw ratio of nanometer rods is adjustable in the 2-50 scope.
6. method according to claim 1 is characterized in that, zinc salt is zinc sulfate, zinc nitrate, zinc acetate or zinc chloride.
7. method according to claim 1 is characterized in that, described germanic acid zinc nanometer rods is under 120-220 ℃ of hydrothermal condition, and germanic acid zinc keeps composition and stable appearance in the pH=0-14 scope.
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| CN106186049A (en) * | 2016-07-14 | 2016-12-07 | 南京大学 | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable |
| CN106881114A (en) * | 2017-03-09 | 2017-06-23 | 济南大学 | A kind of visible light-responded CdS/Cd2Ge2O6The preparation method of heterojunction photocatalyst |
| CN108793231A (en) * | 2018-08-13 | 2018-11-13 | 江苏理工学院 | The method that molten-salt growth method synthesizes fusiform germanic acid zinc nanoparticles |
| CN108956716A (en) * | 2018-08-02 | 2018-12-07 | 吉林大学 | A kind of flexible gas sensor and preparation method thereof based on printable micron linear array sensitive layer |
| CN112537794A (en) * | 2020-11-17 | 2021-03-23 | 欣旺达电动汽车电池有限公司 | Zinc germanate nano material, preparation method thereof and lithium ion battery |
| CN113769766A (en) * | 2021-10-25 | 2021-12-10 | 江南大学 | Preparation method of long afterglow-bismuth based nano composite photocatalyst and application of photocatalyst in degrading agricultural and veterinary medicines |
| CN115739147A (en) * | 2022-06-16 | 2023-03-07 | 江南大学 | Long afterglow/red phosphorus composite material, preparation method thereof and application thereof in degradation of malachite green |
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| CN103586024B (en) * | 2013-11-22 | 2016-01-13 | 武汉理工大学 | A kind of hollow ball or spherical Ag 2znGeO 4the preparation method of photochemical catalyst |
| CN106186049A (en) * | 2016-07-14 | 2016-12-07 | 南京大学 | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable |
| CN106881114A (en) * | 2017-03-09 | 2017-06-23 | 济南大学 | A kind of visible light-responded CdS/Cd2Ge2O6The preparation method of heterojunction photocatalyst |
| CN108956716A (en) * | 2018-08-02 | 2018-12-07 | 吉林大学 | A kind of flexible gas sensor and preparation method thereof based on printable micron linear array sensitive layer |
| CN108793231A (en) * | 2018-08-13 | 2018-11-13 | 江苏理工学院 | The method that molten-salt growth method synthesizes fusiform germanic acid zinc nanoparticles |
| CN112537794A (en) * | 2020-11-17 | 2021-03-23 | 欣旺达电动汽车电池有限公司 | Zinc germanate nano material, preparation method thereof and lithium ion battery |
| CN112537794B (en) * | 2020-11-17 | 2023-04-07 | 欣旺达电动汽车电池有限公司 | Zinc germanate nano material, preparation method thereof and lithium ion battery |
| CN113769766A (en) * | 2021-10-25 | 2021-12-10 | 江南大学 | Preparation method of long afterglow-bismuth based nano composite photocatalyst and application of photocatalyst in degrading agricultural and veterinary medicines |
| CN113769766B (en) * | 2021-10-25 | 2022-08-05 | 江南大学 | Preparation method of long afterglow-bismuth based nano composite photocatalyst and application of photocatalyst in degrading agricultural and veterinary medicines |
| CN115739147A (en) * | 2022-06-16 | 2023-03-07 | 江南大学 | Long afterglow/red phosphorus composite material, preparation method thereof and application thereof in degradation of malachite green |
| CN115739147B (en) * | 2022-06-16 | 2024-03-08 | 江南大学 | Long afterglow/red phosphorus composite material, preparation method thereof and application thereof in malachite green degradation |
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