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CN102962049A - Method for preparing nanometer photocatalytic material via hydrothermal reaction - Google Patents

Method for preparing nanometer photocatalytic material via hydrothermal reaction Download PDF

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CN102962049A
CN102962049A CN201210489103XA CN201210489103A CN102962049A CN 102962049 A CN102962049 A CN 102962049A CN 201210489103X A CN201210489103X A CN 201210489103XA CN 201210489103 A CN201210489103 A CN 201210489103A CN 102962049 A CN102962049 A CN 102962049A
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zinc
reaction
geo
germanate
solution
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闫世成
邹志刚
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Nanjing University
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Nanjing University
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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

A kind of hydro-thermal reaction prepares the method for nano-photocatalyst material
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.
Embodiment 1
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).
Embodiment 4
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).
Embodiment 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.水热反应制备纳米光催化材料的方法,其特征在于步骤包括:将水溶性的锗酸钠和水溶性的锌盐按照Zn:Ge=2:1摩尔比混合;将混合溶液在室温磁力搅拌30-60min后,在80-200℃水热处理3-8h;将反应后的溶液离心、干燥。1. The method for preparing nano photocatalytic material by hydrothermal reaction, it is characterized in that the steps include: mixing water-soluble sodium germanate and water-soluble zinc salt according to Zn:Ge=2:1 molar ratio; magnetically mixing the mixed solution at room temperature After stirring for 30-60 minutes, hydrothermally treat at 80-200° C. for 3-8 hours; centrifuge and dry the reacted solution. 2.根据权利要求1所述的方法,其特征在于,所述离子交换的反应方程式为Na2GeO3+2Zn2+(X)m+H2O=Zn2GeO4+mH- nX+mNanX,其中,X是SO4 2-,NO3 -,CH3COO-或Cl-,且当X为SO4 2-时,m=1,n=2;当X为NO3 -,CH3COO-,Cl-时m=2,n=1。2. The method according to claim 1, characterized in that the ion exchange reaction equation is Na 2 GeO 3 +2Zn 2+ (X) m +H 2 O=Zn 2 GeO 4 +mH - n X+ mNa n X, wherein, X is SO 4 2- , NO 3 - , CH 3 COO - or Cl - , and when X is SO 4 2- , m=1, n=2; when X is NO 3 - , CH 3 COO - , Cl - m=2, n=1. 3.根据权利要求1所述的方法,其特征在于,所述锗酸钠溶液为强碱溶液。3. The method according to claim 1, characterized in that, the sodium germanate solution is a strong alkali solution. 4.根据权利要求2所述的方法,其特征在于,所述离子交换的反应,当X为SO4 2-,NO3 -,Cl-时,该离子交换反应属于强碱制备强酸反应,当X为CH3COO-时,该离子交换反应为强碱制备弱酸反应。4. The method according to claim 2, characterized in that, the reaction of the ion exchange, when X is SO 4 2- , NO 3 - , Cl - , the ion exchange reaction belongs to the reaction of strong base to prepare strong acid, when When X is CH 3 COO - , the ion exchange reaction is a reaction of preparing a weak acid from a strong base. 5.根据权利要求1所述的方法,其特征在于所述锗酸锌材料的显微结构为纳米棒,且纳米棒的长径比在2-50范围内可调。5. The method according to claim 1, characterized in that the microstructure of the zinc germanate material is nanorods, and the aspect ratio of the nanorods is adjustable within the range of 2-50. 6.根据权利要求1所述的方法,其特征在于,锌盐为硫酸锌、硝酸锌、乙酸锌或氯化锌。6. The method according to claim 1, wherein the zinc salt is zinc sulfate, zinc nitrate, zinc acetate or zinc chloride. 7.根据权利要求1所述的方法,其特征在于,所述锗酸锌纳米棒在120-220℃水热条件下,且pH=0-14范围内锗酸锌保持成分和形貌稳定。7 . The method according to claim 1 , wherein the zinc germanate nanorods maintain stable composition and morphology under hydrothermal conditions of 120-220° C. and pH=0-14.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103586024A (en) * 2013-11-22 2014-02-19 武汉理工大学 A kind of preparation method of hollow sphere or spherical Ag2ZnGeO4 photocatalyst
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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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103586024A (en) * 2013-11-22 2014-02-19 武汉理工大学 A kind of preparation method of hollow sphere or spherical Ag2ZnGeO4 photocatalyst
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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Application publication date: 20130313