CN106076306A - The method of template secondary solvent hot preparation ZnO multilevel hierarchy catalysis material - Google Patents

The method of template secondary solvent hot preparation ZnO multilevel hierarchy catalysis material Download PDF

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CN106076306A
CN106076306A CN201610432527.0A CN201610432527A CN106076306A CN 106076306 A CN106076306 A CN 106076306A CN 201610432527 A CN201610432527 A CN 201610432527A CN 106076306 A CN106076306 A CN 106076306A
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catalysis material
template
multilevel hierarchy
secondary solvent
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CN106076306B (en
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苏碧桃
董永永
王芳萍
靳正娟
董娜
何方振
莘俊莲
王其召
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Heze Smart New Material Technology Co ltd
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Northwest Normal University
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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    • 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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    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/30—Particle morphology extending in three dimensions
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    • C01P2004/34—Spheres hollow

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Abstract

A kind of method that the invention provides template secondary solvent hot preparation ZnO multilevel hierarchy catalysis material, is that pretreated Folium Ginkgo is immersed Zn (CH3COO)2·2H2In the dehydrated alcohol of O, transfer in autoclave, at 160 ~ 200 DEG C, react 8 ~ 10 h；Reaction drains dehydrated alcohol after terminating, and is dried, obtains presoma；Again presoma is removed template in 550 ~ 750 DEG C of calcining 1.0 ~ 2.0 h, obtain ZnO multi-level nano-structure catalysis material.This material has hollow, loose structure, plays multiple action in photocatalytic process: can active adsorption activated reactant molecule, effectively absorb radiant light, thus its photocatalysis efficiency can be effectively improved.Photocatalytic degradation experiment shows, this multilevel hierarchy ZnO catalysis material has higher photocatalytic activity, has good degradation effect to methylene blue, therefore has good application prospect in terms of degradation of dye.

Description

The method of template secondary solvent hot preparation ZnO multilevel hierarchy catalysis material
Technical field
The present invention relates to the preparation of a kind of ZnO nano catalysis material, particularly relate to a kind of template secondary solvent hot preparation The method of ZnO multilevel hierarchy catalysis material, is mainly used in the aspects such as degradation of organic dyes, sewage disposal, air cleaning.
Background technology
ZnO is commonly called as zinc white, is the direct semiconductor material with wide forbidden band (energy gap for wurtzite structure under a kind of room temperature 3.37 eV), its exciton bind energy is 60 meV, can produce light induced electron-sky under wavelength irradiates less than 378 nm ultraviolet lights Cave pair.There is the advantage such as low cost, heliosensitivity is good, oxidisability is strong, avirulence and excellent chemical stability, be a kind of good Photocatalyst material.Nano-ZnO owing to particle diameter is little, specific surface area big, and can effectively the advantage such as degradating organic dye exist Photocatalysis field has a wide range of applications.Research shows, the photocatalysis performance of ZnO nano material not only has with its size Close, and its pattern plays vital effect to performance.At present, the preparation method of ZnO nano material has a lot, as molten Glue-gel method, the sedimentation method, solvent-thermal method etc..Mostly there is respective deficiency in traditional preparation methods, as of a great variety in agents useful for same, Manufacturing cycle length, cost are high, be easily generated environmental pollution etc..
Template is the very important technology of one of synthesizing nano compound material, utilizes its space confinement effect and structure The size of synthetic material, pattern, structure and arrangement etc. can effectively be modulated, before having wide application by guide effect Scape.In nature, multiple natural biomass contains baroque inorganic nano material or organic nano material, and these biologies are received The physical dimension height of rice material is homogeneous, and has the feature of structure diversity.Therefore, natural biomass is to prepare structure complexity And the preferable template of nano material that particle diameter shows a monodisperse distribution.Semen Ginkgo is that China's ice age distinctive fourth season is lonely moves tree Kind, enjoy living fossil, national treasure, the good reputation of state tree.It has stronger adaptive capacity to environment and anti-adversity ability, can plant in China Scope is the most wide.Folium Ginkgo (GL) is mainly by vein, mesophyll and epidermis three part composition.Blade is divided into countless little by vein Block, each fritter has thready pulse vein end to stretch into, and forms the transport channel in blade.Its main component has C, H, O etc..GL Typically all going out of use, this not only causes environmental pollution, and also results in the wasting of resources.If with GL as template, carry out target material Preparation, vanelets numerous in GL has special construction, can give the special structure of target material and premium properties, and Can be with twice laid.
Summary of the invention
It is an object of the invention to provide a kind of side preparing ZnO multi-level nano-structure catalysis material with Folium Ginkgo for template Method.
One, the preparation of ZnO multi-level nano-structure catalysis material
With Zn (CH3COO)2·2H2O is raw material, and Folium Ginkgo (GL) is template, and ethanol is solvent, utilizes template secondary solvent full-boiled process Prepare.Its concrete technology is as follows:
(1) pretreatment of Folium Ginkgo
By Folium Ginkgo (GL) with water clean remove surface impurity, after carry out Soxhlet reflow treatment with water and dehydrated alcohol, dry standby With.The volume ratio of water and dehydrated alcohol is 1:1 ~ 1:1.3；Return time is 12 ~ 16 h.
(2) preparation of presoma ZnO/GL
By Zn (CH3COO)2·2H2O and being added sequentially in dehydrated alcohol through the GL of above-mentioned process, transfers to politef high In pressure reactor, at 160 ~ 200 DEG C, react 8 ~ 10 h；Reaction drains dehydrated alcohol after terminating, and is dried, obtains presoma, be designated as ZnO/GL.GL Yu Zn (CH after process3COO)2·2H2The mass ratio of O is 0.139:1 ~ 0.278:1.
(3) preparation of ZnO multi-level nano-structure catalysis material
Presoma ZnO/GL is placed in Muffle furnace, in 550 ~ 750 DEG C of calcining 1.0 ~ 2.0 h to remove GL template, obtains ZnO Multi-level nano-structure catalysis material.
Two, the structural characterization of ZnO catalysis material
Sample structure, the pattern prepared the present invention below with means such as XRD, SEM, TEM characterize.
1, XRD characterizes
Fig. 1 is that the sample ZnO-2(for preparing of the present invention is with the presence of template) and ZnO-0(exist without template) XRD figure (a) and Partial enlarged drawing (b).As seen from Figure 1, all diffraction maximums and wurtzite-type ZnO standard card (JCPDS in XRD spectra 361451) fit like a glove.The relatively XRD figure of ZnO-0 and ZnO-2 finds: have material ZnO-2 obtained under template existence condition Diffraction peak intensity compared with without resulting materials ZnO-0 weak under the conditions of template, diffraction maximum is significantly broadened, and to the high angle of diffraction (2 θ) side To there occurs displacement.The existence of this one side pattern of descriptive parts GL limits the oriented growth of the little crystal grain of ZnO, table in XRD figure is composed Now for diffraction peak intensity weaken (crystal property reduction) and widthization (size reduction).According to Debye-Scherrer formula (d =k λ/ βCos θ) size of crystal grain in sample ZnO-0 and ZnO-2 can be calculated it is respectively 35,29 nm.On the other hand, In the diffraction maximum displacement explanation sample ZnO-2 to the high angle of diffraction (2 θ) direction, the unit cell volume of ZnO reduces.It can thus be seen that The effect of template restricted target material size.
2, SEM figure characterizes
Fig. 2 is sample ZnO-0(a prepared by the present invention), ZnO-2(b) SEM figure.From figure a it will be seen that sample ZnO-0 be by Many nanometer little granule compositions, and the sample ZnO-2 prepared by means of template GL is hollow spheres, ball wall is by a large amount of nanometers Grain assembles (figure b).
3, TEM figure characterizes
Fig. 3 is sample ZnO-0(a prepared by the present invention) and ZnO-2(b) TEM figure.From figure a it can be seen that sample ZnO-0 Granular size uneven, in irregular shape, and have obvious agglomeration.But spherical sample ZnO-prepared by template The size of 2 is highly uniform (see figure b illustration).Additionally, be can be seen that the hollow of microsphere and ball wall are many by the TEM picture of this sample Pore structure.By illustration it is observed that hexagonal (this result one with XRD of the nano-particle that forms microsphere in sample ZnO-2 Cause), size is uniform.
From SEM and tem observation to, ZnO nano material prepared by the present invention has hollow, loose structure, and we are referred to as the most Level structure, this structure will play multiple action in photocatalytic process: can active adsorption activated reactant molecule, have Effect absorbs radiant light, thus can be effectively improved its photocatalysis efficiency.
Three, the Photocatalytic Degradation Property of ZnO catalysis material
Enter below with the photocatalytic degradation of methylene blue (MB) the solution photocatalysis performance of sample prepared by the present invention that decolours Row analytic explanation.
Photocatalytic degradation decolorization experiment: by 40 mg sample dispersion in 40 mL concentration be 20 mg L-1Methylene blue (MB) in solution；Stir 0.5 h in the dark state, after reaching suction-de-balance, under the conditions of 300 W mercury lamps (ML) irradiate, carry out light urge Change degradation and decolorization experiment；Sampling 5 mL every 2 min, solid sample is removed in centrifugation immediately.With on spectrophotometric determination Layer clear liquid is at the maximum absorption wavelength of 664 nm(MB) absorbance at placeA t, with MB solution percent of decolourization on sampleD t % ~ tWith ln (C 0 /C t) ~ tStudy the degradation kinetics behavior on its surface of its photocatalysis performance and MB molecule.
Percent of decolourization utilizes formula:D t (%) = [(A 0-A t)/A 0] × (100%) calculate.Wherein,A 0WithA tRespectively For the initial of MB solution and light application time it istTime absorbance.
1, the calcining heat impact on MB solution degradation decoloration performance
Fig. 4 a is the dyestuff MB solution degradation decolouring of different temperatures (550 ~ 750 DEG C) calcining gained sample ZnO-550 ~ 750 pairD t % ~tResult.It can be clearly seen that under the conditions of the irradiation of 300 W ML, all samples degradation and decolorization to MB solution It is respectively provided with obvious action.And in the range of investigating, along with the rising of calcining heat, reach optimal when 650 DEG C；When When calcining heat continues to raise, its photocatalysis performance decreases again.Figure b is that dyestuff MB solution degradation is decoloured by sample ZnO Dynamic behavior.By figure b it will be seen that MB solution degradation and decolorization on all samples the most reasonable obedience first order kinetics Behavior ln (C 0/C t) = k 1 t, and by ln (C 0/C t) ~tThe slope of straight line can obtain first order kinetics speed constantk 1(T) (see Table 1).ZnO-650(650 DEG C of sample calcining gained sample ZnO) photocatalytic activity be approximately ZnO-550(550 DEG C of sample Calcining gained sample ZnO) 2 times.
2, the calcination time impact on MB solution degradation decoloration performance
Fig. 5 a is the dyestuff MB solution degradation decolourings of different calcination time (1.0,1.5,2.0 h) gained sample ZnO-1.0 ~ 2.0 pair Ln (C 0/C t) ~ tResult.It can be clearly seen that be similar to the impact of calcining heat, the photocatalytic activity of sample with The increasing in first increasing the trend reduced afterwards of calcination time, when about 1.5 h, it is active most preferably.Same MB solution is in difference The degradation and decolorization the most reasonable obedience first order kinetics behavior ln of calcination time (1.0,1.5,2.0 h) gained sample ZnO (C 0/C t)= k 1(see Fig. 5 b), and by ln (C 0/C t) ~ tThe slope of straight line can obtain first order kinetics speed constantk 1(t) (ZnO-1.0 ~ 2.0) (see Table 1).The photocatalytic activity of sample ZnO-1.5 is approximately 1.3 times of sample ZnO-1.0.Fromk 1(t) It can be seen that calcination time is less than calcining heat to the influence degree of sample photocatalysis performance.
3, the template consumption impact on MB solution degradation decoloration performance
The addition of Control architecture GL, with GL Yu Zn (CH3COO)2·2H2The mass ratio of O be respectively 0.000:1,0.139:1, 0.236:1,0.250:1,0.278:1, solvent thermal reaction condition is constant, carries out under optimal calcination condition (650 DEG C, 1.5 h) Heat treatment, the sample obtained is respectively labeled as ZnO-0,1,2,3,4.
Fig. 6 a is the dyestuff MB solution degradation decolourings of sample ZnO-0 ~ 4 pairD t %~ tResult.It can be clearly seen that institute There is sample that the degradation and decolorization of MB solution is respectively provided with obvious action.But, utilize ZnO material prepared by template (ZnO-1 ~ 4) photocatalytic activity is significantly higher than without preparing sample (ZnO-0) under the conditions of template, and with the increase of template consumption, the light of sample is urged Change activity in first increasing the variation tendency reduced afterwards；As template GL and Zn (CH3COO)2·2H2The mass ratio of O is that 0.236:1 is attached Time near, the photocatalysis performance of prepared sample is optimal.
Fig. 6 b give MB solution ln on sample ZnO-0 ~ 4 (C 0/C t) ~ tResult.It will be seen that MB solution Degradation and decolorization the most reasonable obedience first order kinetics behavior ln on all samples (C 0/C t) = k 1 t, and by ln (C 0 /C t) ~ tThe slope of straight line can obtain first order kinetics speed constantk 1(ZnO-0 ~ 4) (are shown in Table 2).Shown by table 2: GL Yu Zn (CH3COO)2·2H2When the mass ratio of O is respectively 0.236:1, the photocatalytic activity preparing sample ZnO-2 is approximately without mould Under slat element nearly 6 times of sample ZnO-0.
Shown by the data of table 2, when template GL amount ratio is bigger, enter into the Zn in GL blade2+Relatively decentralized, by forging Nanometer powder in the case of gained sample is similar to without template when burn off goes template；During along with the reduction of template consumption, forging The ZnO nano granule that burn off is formed after going template will be interconnected to form Nano/micron sheet, and this Nano/micron sheet is cooled The stress produced due to its both sides in journey is different and crimps, thus forms aforesaid hollow ball, and its wall presents porous Structure (is called multilevel hierarchy).Along with the continuation of template consumption reduces, in sample, substantial amounts of ZnO nano granule is mutually piled up, So that ball wall is fine and close, hole minimizing/little.Therefore, the photocatalysis performance of sample ZnO-0 ~ 4 should mainly and the size of sample, Pattern/structure is relevant.The size of material is the least, specific surface area is the biggest, absorption property is the best, catalytic performance is the best.More important : the multilevel hierarchy of sample not only contributes to the fully absorption of reactant molecule, activation, and to light by suction repeatedly Receive-reflection-absorb and effectively absorb, thus ensure that the photocatalytic activity that sample is high.
In sum, hinge structure of the present invention has the advantage that
1, the present invention is with Zn (CH3COO)2·2H2O, GL are raw material, use template secondary solvent full-boiled process, are prepared for having multistage knot The ZnO catalysis material of structure-porous hollow microsphere, has higher photocatalytic activity, has the widest in terms of degradation of dye Wealthy application prospect；
2, the properity of ZnO catalysis material of the present invention can by regulation and control calcining heat, calcination time, the consumption of Folium Ginkgo, Thus ensure that the multilevel hierarchy of ZnO nano catalysis material and good photocatalysis performance；
3, the preparation method of the present invention is without other any additive, not only simplify preparation technology, reduces cost, topmost It is twice laid, environmental protection.
Accompanying drawing explanation
Fig. 1 is XRD figure (a) and the partial enlarged drawing (b) thereof of sample ZnO-0 and ZnO-2.
Fig. 2 is sample ZnO-0(a), ZnO-2(b) and ZnO-3(c) SEM figure.
Fig. 3 is sample ZnO-0(a), ZnO-2(b) TEM figure.
Fig. 4 is different calcining heat gained sample ZnO-550 ~ 750 pair dyestuff MB solution degradation decolorizing effect figure (a) and moves Mechanical behavior (b).
Fig. 5 is different calcination time gained sample ZnO-1.0 ~ 2.0 pair dyestuff MB solution degradation decolorizing effect figure (a) and moves Mechanical behavior (b).
Fig. 6 is different templates consumption gained sample ZnO-0 ~ 4 pair dyestuff MB solution degradation decolorizing effect figure (a) and kinetics Behavior (b).
Detailed description of the invention
Below by specific embodiment, preparation and the photocatalysis performance thereof of ZnO multilevel hierarchy catalysis material of the present invention are made Further illustrate.
Embodiment 1
(1) pretreatment of GL: GL use water is cleaned after removing surface impurity, by the water that volume ratio is 1:1 and dehydrated alcohol Soxhlet Reflux 16 h, dries standby；
(2) preparation of ZnO multilevel hierarchy catalysis material: by GL(processed for 0.5000 g with GL Yu Zn (CH3COO)2· 2H2The mass ratio of O is expressed as 0.139:1) immerse 3.6000 g Zn (CH3COO)2·2H2In the ethanol solution of O, transfer to gather In tetrafluoroethene autoclave, at 200 DEG C, react 10 h；Reaction drains solvent after terminating, and is dried, obtains precursor material, note For ZnO/GL；ZnO/GL is calcined at 550 DEG C 2 h to remove GL template, obtain ZnO nano catalysis material sample (ZnO- 550).Sample reacts 12 min under 300 W mercury lamps and the methylene blue degradation rate of 20 mg/L is reached 71.3%.
Embodiment 2
Calcination condition is: temperature 650 DEG C, the other the same as in Example 1.The ZnO nano catalysis material (ZnO-650) obtained is 300 React 12 min under W mercury lamp and the methylene blue degradation rate of 20 mg/L is reached 91.2%.
Embodiment 3
Calcination condition is: temperature 750 DEG C, the other the same as in Example 1.The ZnO nano catalysis material (ZnO-750) obtained is 300 React 12 min under W mercury lamp and the methylene blue degradation rate of 20 mg/L is reached 74.5%.
Embodiment 4
Calcining heat is 650 DEG C, and calcination time is 1.0 h, the other the same as in Example 1.The ZnO nano catalysis material obtained (ZnO-1.0) under 300 W mercury lamps, react 12 min and the methylene blue degradation rate of 20 mg/L is reached 88.5%.
Embodiment 5
Calcining heat is 650 DEG C, and calcination time is 1.5 h, the other the same as in Example 1.The ZnO nano catalysis material obtained (ZnO-1.5) under 300 W mercury lamps, react 12 min and the methylene blue degradation rate of 20 mg/L is reached 93.9%.
Embodiment 6
Calcining heat is 650 DEG C, and calcination time is 1.5 h, and template consumption becomes 0.5000 g respectively, other the most same embodiment 1.Obtain ZnO nano catalysis material (ZnO-1) under 300 W mercury lamps, react 12 min methylene blue degraded to 20 mg/L Rate reaches 93.9%.
Embodiment 7
Calcining heat is 650 DEG C, and calcination time is 1.5 h, and template consumption becomes 0.8500 g respectively, other the most same embodiment 1.Obtain ZnO nano catalysis material (ZnO-2) under 300 W mercury lamps, react 12 min methylene blue degraded to 20 mg/L Rate reaches 96.6%.
Embodiment 8
Calcining heat is 650 DEG C, and calcination time is 1.5 h, and template consumption becomes 0.9000 g respectively, other the most same embodiment 1.Obtain ZnO nano catalysis material (ZnO-3) under 300 W mercury lamps, react 12 min methylene blue degraded to 20 mg/L Rate reaches 89.5%.
Embodiment 9
Calcining heat is 650 DEG C, and calcination time is 1.5 h, and template consumption becomes 1.0000 g respectively, other the most same embodiment 1.Obtain ZnO nano catalysis material (ZnO-4) under 300 W mercury lamps, react 12 min methylene blue degraded to 20 mg/L Rate reaches 85.2%.

Claims (6)

1. the method for template secondary solvent hot preparation ZnO multilevel hierarchy catalysis material, is with Zn (CH3COO)2·2H2O is former Material, Folium Ginkgo is template, and ethanol is solvent, utilizes template secondary solvent full-boiled process to prepare.
2. the method for template secondary solvent hot preparation ZnO multilevel hierarchy catalysis material as claimed in claim 1, its feature exists In: pretreated Folium Ginkgo is immersed Zn (CH3COO)2·2H2In the dehydrated alcohol of O, transfer to politef high pressure anti- Answer in still, at 160 ~ 200 DEG C, react 8 ~ 10 h；Reaction drains dehydrated alcohol after terminating, and is dried, obtains presoma；Again by forerunner Body is placed in Muffle furnace, in 550 ~ 750 DEG C of calcining 1.0 ~ 2.0 h to remove Folium Ginkgo template, obtains ZnO multi-level nano-structure Catalysis material.
3. the method for template secondary solvent hot preparation ZnO multilevel hierarchy catalysis material as claimed in claim 1, its feature exists In: the pretreatment of Folium Ginkgo, is to clean Folium Ginkgo water to remove surface impurity, and rear water and dehydrated alcohol are with 1:1 ~ 1:1.3 Volume ratio carry out Soxhlet reflow treatment 12 ~ 16 h, dry standby.
4. the method for template secondary solvent hot preparation ZnO multilevel hierarchy catalysis material, its feature as described in Claims 2 or 3 It is: Folium Ginkgo after pretreatment and Zn (CH3COO)2·2H2The mass ratio of O is 0.139:1 ~ 0.278:1.
5. the preparation method of ZnO multilevel hierarchy catalysis material as claimed in claim 4, it is characterised in that: after pretreatment GL Yu Zn (CH3COO)2·2H2The mass ratio of O is 0.236:1.
6. the method for template secondary solvent hot preparation ZnO multilevel hierarchy catalysis material as claimed in claim 5, its feature exists In: the calcining heat of described removing template is 650 DEG C, and calcination time is 1.5 h.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110449168A (en) * 2019-08-02 2019-11-15 南京理工大学 Hollow tubular ZnO loads bismuth molybdate and cadmium sulfide carries out the composite material and preparation method of concerted catalysis
CN114367280A (en) * 2022-01-20 2022-04-19 吉林化工学院 Rose-type ZnO photocatalytic material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103736442A (en) * 2014-01-10 2014-04-23 东南大学 Method for preparing porous alumina composite material through biological template method
CN105344322A (en) * 2015-12-03 2016-02-24 西北师范大学 Method for preparing biological activated carbon from waste maidenhair tree leaves and folium ginkgo herb residue

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103736442A (en) * 2014-01-10 2014-04-23 东南大学 Method for preparing porous alumina composite material through biological template method
CN105344322A (en) * 2015-12-03 2016-02-24 西北师范大学 Method for preparing biological activated carbon from waste maidenhair tree leaves and folium ginkgo herb residue

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LEI HAN ET AL.: "Leaf-templated synthesis of 3D hierarchical porous cobalt oxide nanostructure as direct electrochemical biosensing interface with enhanced electrocatalysis", 《BIOSENSOER AND BIOELECTRONICS》 *
张莹: "ZnO纳米材料微结构设计、制备与气敏性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110449168A (en) * 2019-08-02 2019-11-15 南京理工大学 Hollow tubular ZnO loads bismuth molybdate and cadmium sulfide carries out the composite material and preparation method of concerted catalysis
CN114367280A (en) * 2022-01-20 2022-04-19 吉林化工学院 Rose-type ZnO photocatalytic material and preparation method and application thereof
CN114367280B (en) * 2022-01-20 2024-03-12 吉林化工学院 Rose type ZnO photocatalytic material and preparation method and application thereof

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