CN108408761B - The controllable method for preparing of three-dimensional honeycomb structure ZnO nano material - Google Patents
The controllable method for preparing of three-dimensional honeycomb structure ZnO nano material Download PDFInfo
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Abstract
The invention discloses a kind of controllable method for preparing of three-dimensional honeycomb structure ZnO nano material, comprising: (1) preparation of nano carbon microsphere；(2) nano carbon microsphere is impregnated in deionized water, coating reaction bottom liquid is made；It is adjusted with acid the pH value of coating reaction bottom liquid；(3) zinc solution and aqueous slkali are slowly dropped into the liquid of coating reaction bottom with certain speed ratio simultaneously respectively, it controls pH value in reaction and reaction temperature is constant, and coating reaction bottom liquid is stirred, reaction is completed and after centrifugation, washing, drying, is made Zn (OH)2/ carbon ball composite material；(4) by Zn (OH)2The calcining of/carbon ball composite material, obtains three-dimensional honeycomb structure ZnO nano material.Large specific surface area, the surface-active of three-dimensional honeycomb structure ZnO nano material prepared by the present invention are strong, can effectively improve the air-sensitive and photocatalysis performance of material；The present invention is at low cost, yield is high, stability is good, pollution-free, is expected to be widely applied in air-sensitive, photocatalysis field.
Description
Technical field
The present invention relates to a kind of controllable method for preparing of three-dimensional honeycomb structure nano zinc oxide material, belong to high-performance inorganic
Nonmetallic technical field of function materials.
Background technique
Zinc oxide is a kind of high performance semiconductor functional material, has excellent catalysis, optics, magnetics, electrology characteristic,
And physicochemical properties are stable, environmental-friendly, are widely used in the numerous areas such as ceramics, chemical industry, electronics, optics, biology.Especially
It is when the scale of Zinc oxide particles is in nanometer scale, and material has large specific surface area and high surfaces activity, often quilt
As gas sensitive, catalyst etc., play an important role in terms of gas-monitoring, environmental improvement.But nano grain surface
It is high-performance, cause nano zine oxide to be easy to reunite at work, make that its specific surface area reduces, surface reaction activity site subtracts
It is few, to influence its reactivity, limit air-sensitive and catalytic effect.To solve this problem, people are often negative by noble metal
It carries, special appearance (huge linear, the band-like, petal-shaped of such as specific surface area, honeycomb) approach increases nano zine oxide
Surface reaction activity bit number of points at work, and then improve the reactivity of material.
" chemical research " 2007,18 (1): 23-27 discloses one, and " hydrothermal synthesis and the pattern control of ZnO crystallite are ground
Study carefully ", hydro-thermal method is used in the paper, and at low temperature by changing precursor concentration, reaction time and reaction temperature, flower has been made
Shape, honeycomb, columnar ZnO crystallite；But prepared honeycomb ZnO scale is larger in the paper, belongs to micron order, is unable to satisfy height
The requirement of performance air-sensitive and catalysis material." Institutes Of Chifeng's journal (natural science edition) " 2010,26 (7): 106-107 discloses one
" hydrothermal synthesis, characterization and the field emission characteristic of different shape zinc oxide nanostructure ", in the paper, using improved hydro-thermal
Method has synthesized zinc-oxide nano by parameters such as control reaction solution concentration, reaction temperature and reaction time on the glass substrate
The nanostructures such as stick array, honeycomb-shaped oxidizing zinc nanometer rods, flower shape zinc oxide nanometer rods；But prepared honeycomb oxygen in the paper
Change Zinc material is the rodlike cross structure of two-dimensional nano, has not yet been formed three-dimensional honeycomb shape cellular structure, surface reaction activity site compared with
It is few.The Chinese invention patent application that publication No. in 2017 is CN107321347A discloses a kind of honeycomb-shaped oxidizing zinc nm wall battle array
The preparation method of column, this method is using aluminium foil as substrate, first by radio frequency magnetron method in substrate sputter seed layer, then utilizes water
Thermal method reaction, obtains honeycomb-shaped oxidizing zinc nm wall array；But the honeycomb diameter of honeycomb-shaped oxidizing Zinc material prepared by this method
For micron order, reactivity larger compared with specific surface area for nanoscale honeycomb is limited, and honeycomb scale should not be flexibly controllable.
Summary of the invention
It is excellent it is an object of the invention to solve at least the above problems and/or defect, and provide at least to will be described later
Point.
In order to realize these purposes and other advantages according to the present invention, a kind of three-dimensional honeycomb structure ZnO nanometer is provided
The controllable method for preparing of material, comprising the following steps:
Step 1: carbon source material is dissolved in deionized water, it is configured to the carbon source material solution that concentration is 0.1~1mol/L；
It transfers them in hydrothermal reaction kettle, 1~6h is reacted at 140~240 DEG C；Through washing, 60 DEG C of drying after cooling, nanometer is obtained
Carbon ball；
Step 2: the nano carbon microsphere of step 1 is immersed in deionized water in the ratio that solid-liquid mass ratio is 1:50~1:20
In, coating reaction bottom liquid is made；It is adjusted with acid the pH value of coating reaction bottom liquid；
Step 3: respectively by concentration be 0.1~1mol/L zinc solution and mass concentration be 5~10% aqueous slkali it is same
When be slowly dropped into the coating reaction bottom liquid of step 2 with the speed ratio of 2:1~5:1, it is permanent to control pH value in reaction and reaction temperature
It is fixed, and coating reaction bottom liquid is stirred, reaction is completed and after centrifugation, washing, 50~70 DEG C of drying, is made Zn (OH)2/
Carbon ball composite material；
Step 4: by the Zn (OH) of step 32/ carbon ball composite material obtains three-dimensional bee in 550~750 DEG C of 1~3h of calcining
Nest structure ZnO nano material.
Preferably, the carbon source material is glucose, fructose, sucrose, maltose, pectin, starch, cellulose, konjaku
Any one in Glucomannan.
Preferably, the acid in the step 2 is acetic acid, hydrochloric acid, sulfuric acid, any one in phosphoric acid；It is adjusted with acid packet
The pH value of reaction bottom liquid is covered to 4~7.
Preferably, the zinc solution is acetic acid zinc solution, zinc nitrate solution, liquor zinci chloridi, zinc sulfate, zinc oxalate
Any one in solution.
Preferably, the aqueous slkali is weak aqua ammonia, urea liquid, sodium carbonate liquor, sodium bicarbonate solution, ammonium hydrogen carbonate
Solution, sal volatile, any one in sodium hydroxide solution.
Preferably, in the step 3, control pH value in reaction is 4~7；Reaction temperature is 20~40 DEG C.
Preferably, in the step 3, during the reaction, apply ultrasound into coating reaction bottom liquid, while to packet
It covers in reaction bottom liquid and is passed through nitrogen；The flow velocity of the nitrogen is 150~250mL/min；The frequency of the ultrasound be 30~
45KHz, ultrasound use intermitant irradiation, and intermittent time when intermitant irradiation is 15~20s/5~10s.
Preferably, in the step 1, before washing further include: stainless steel ball is added in the feed liquid after reaction and is described
In device, while the ethyl alcohol of material liquid volume 1/3 is added, seals, and the spherical container after sealing is placed on four axis bevellers, opens
Four axis bevellers drive stainless steel spherical container randomly to rotate 30~60min；The feed inlet of the stainless steel spherical container passes through
Threaded cap sealing, threaded cap flush after being tightly connected with the surface of stainless steel spherical container；The shaft of the four axis beveller turns
Speed is 150~200rpm, and stochastic transition frequency is 10~20s.
Preferably, process is carried out the following processing to nano carbon microsphere obtained in the step 1: nano carbon microsphere is sent into
In atmos low-temperature plasma device, make nano carbon microsphere be in 20 at the jet exit of atmos low-temperature plasma~
60mm, the throughput in atmos low-temperature plasma device according to 5~15L/h are passed through gas, apply operating voltage, are formed
Plasma jet controls the movement speed of the jet exit of atmos low-temperature plasma device in 5~15mm/s, make etc. from
The injection of daughter jet stream handles 60~90min to nano carbon microsphere on nano carbon microsphere；The operating voltage uses high-voltage ac power
It provides, the operating voltage is the alternating voltage of 35~100kV, and frequency is 100~300kHz；The gas is air, rare
The mixing of one or more of gas/oxygen, oxygen, nitrogen, ammonia.
Preferably, the process calcined in the step 4 are as follows: by Zn (OH)2Rotary calcination is added in/carbon ball composite material
In furnace, 100~300 DEG C are heated to the speed of 3~5 DEG C/min, 10~30min is kept the temperature, then with 1~2.5 DEG C/min
Speed be heated to 400~500 DEG C, keep the temperature 30~60min, be then heated to the speed of 0.5~1 DEG C/min
550~750 DEG C, 60~90min is kept the temperature, three-dimensional honeycomb structure ZnO nano material is obtained；The rotation speed of the rotary roasting furnace
For 5~10r/min.
The present invention is include at least the following beneficial effects:
(1) present invention can adjust the partial size and honeycomb size of prepared nano carbon microsphere by the condition of change hydro-thermal reaction,
Realize the controllable preparation to three-dimensional honeycomb structure ZnO nano material；
(2) large specific surface area, the surface-active of the three-dimensional honeycomb structure ZnO nano material prepared by the present invention are strong, can have
Effect improves the air-sensitive and photocatalysis performance of material；
(3) present invention is at low cost, yield is high, stability is good, pollution-free, is expected to be promoted in air-sensitive, photocatalysis field
Using.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention:
Fig. 1 is the scanning electron microscope (SEM) photograph of three-dimensional honeycomb structure ZnO nano material prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of nano carbon microsphere prepared by the embodiment of the present invention 1；
Fig. 3 is the X ray diffracting spectrum of three-dimensional honeycomb structure ZnO nano material prepared by the embodiment of the present invention 1；
Fig. 4 is the ultraviolet catalytic degradation methylene of three-dimensional honeycomb structure ZnO nano material prepared by the embodiment of the present invention 1
Blue curve graph.
Specific embodiment:
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text
Word can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
Embodiment 1:
A kind of controllable method for preparing of three-dimensional honeycomb structure ZnO nano material, comprising the following steps:
Step 1: glucose is dissolved in deionized water, it is configured to the glucose solution that concentration is 0.5mol/L；It is shifted
Into hydrothermal reaction kettle, 4h is reacted at 180 DEG C；Through washing, 60 DEG C of drying after cooling, the single of particle size about 80nm is made
The nano carbon microsphere of property, favorable dispersibility；Fig. 2 is the scanning electron microscope (SEM) photograph of nano carbon microsphere prepared by embodiment 1；
Step 2: the nano carbon microsphere of step 1 is impregnated in deionized water in the ratio that solid-liquid mass ratio is 1:30, system
Obtain coating reaction bottom liquid；The pH value of coating reaction bottom liquid is adjusted to 5.6 with acetic acid；
Step 3: respectively by concentration be 1mol/L acetic acid zinc solution 100mL and mass concentration be 7% weak aqua ammonia simultaneously
It is slowly dropped into the coating reaction bottom liquid of step 2 with the speed ratio of 4:1, control pH value in reaction is 5.6 and reaction temperature is 25
DEG C, and coating reaction bottom liquid is stirred, reaction is completed and after centrifugation, washing, 60 DEG C of drying, is made Zn (OH)2/ carbon ball
Composite material；The mass volume ratio of nano carbon microsphere and zinc solution in the liquid of the coating reaction bottom is 1:100；The zinc acetate
The rate of addition of solution is 3mL/min；
Step 4: by the Zn (OH) of step 32/ carbon ball composite material removes nano carbon microsphere in 600 DEG C of calcining 1h, obtains three
Tie up honeycomb ZnO nano material；Through detecting the honeycomb size for the three-dimensional honeycomb structure ZnO nano material that the embodiment obtains about
For 80nm；Specific surface area 300m2/g；Wherein, Fig. 1 shows sweeping for the three-dimensional honeycomb structure ZnO nano material of the preparation of embodiment 1
Retouch electron microscope；Fig. 3 shows the X ray diffracting spectrum of the three-dimensional honeycomb structure ZnO nano material of the preparation of embodiment 1, through retrieving,
All diffraction maximums occurred in the XRD spectrum of product belong to the ZnO of hexagonal structure, the corresponding ZnO diffraction of each diffraction maximum
Veil is respectively (100), (002), (101), (102), (110), (103), (200) (112), (004), (202), it may be determined that is produced
Object is the ZnO of hexagonal structure, and no other impurity or miscellaneous phase exist.
Embodiment 2:
A kind of controllable method for preparing of three-dimensional honeycomb structure ZnO nano material, comprising the following steps:
Step 1: glucose is dissolved in deionized water, it is configured to the glucose solution that concentration is 0.25mol/L；By its turn
It moves in hydrothermal reaction kettle, reacts 4h at 160 DEG C；Through washing, 60 DEG C of drying after cooling, the list of particle size about 60nm is made
The nano carbon microsphere of one property, favorable dispersibility；
Step 2: the nano carbon microsphere of step 1 is impregnated in deionized water in the ratio that solid-liquid mass ratio is 1:40, system
Obtain coating reaction bottom liquid；The pH value of coating reaction bottom liquid is adjusted to 6.0 with acetic acid；
Step 3: respectively by concentration be 0.5mol/L acetic acid zinc solution 100mL and mass concentration be 5% weak aqua ammonia it is same
When be slowly dropped into the coating reaction bottom liquid of step 2 with the speed ratio of 5:1, control pH value in reaction is 6.0 and reaction temperature is 30
DEG C, and coating reaction bottom liquid is stirred, reaction is completed and after centrifugation, washing, 60 DEG C of drying, is made Zn (OH)2/ carbon ball
Composite material；The mass volume ratio of nano carbon microsphere and zinc solution in the liquid of the coating reaction bottom is 1:100；The zinc acetate
The rate of addition of solution is 3mL/min；
Step 4: by the Zn (OH) of step 32/ carbon ball composite material obtains three-dimensional honeycomb structure in 650 DEG C of calcining 1h
ZnO nano material；Honeycomb size through detecting the three-dimensional honeycomb structure ZnO nano material that the embodiment obtains is about 60nm；Than
Surface area 410m2/g。
Embodiment 3:
A kind of controllable method for preparing of three-dimensional honeycomb structure ZnO nano material, comprising the following steps:
Step 1: sucrose is dissolved in deionized water, it is configured to the sucrose solution that concentration is 1mol/L；Transfer them to hydro-thermal
In reaction kettle, 5h is reacted at 200 DEG C；Through washing, 60 DEG C of drying after cooling, the unicity of particle size about 90nm is made, divides
Dissipate the good nano carbon microsphere of property；
Step 2: the nano carbon microsphere of step 1 is impregnated in deionized water in the ratio that solid-liquid mass ratio is 1:50, system
Obtain coating reaction bottom liquid；The pH value of coating reaction bottom liquid is adjusted to 6.5 with acetic acid；
Step 3: respectively by concentration be 1mol/L acetic acid zinc solution 100mL and mass concentration be 10% weak aqua ammonia it is same
When be slowly dropped into the coating reaction bottom liquid of step 2 with the speed ratio of 3:1, control pH value in reaction is 6.5 and reaction temperature is 35
DEG C, and coating reaction bottom liquid is stirred, reaction is completed and after centrifugation, washing, 60 DEG C of drying, is made Zn (OH)2/ carbon ball
Composite material；The mass volume ratio of nano carbon microsphere and zinc solution in the liquid of the coating reaction bottom is 1:100；The zinc acetate
The rate of addition of solution is 4mL/min；
Step 4: by the Zn (OH) of step 32/ carbon ball composite material obtains three-dimensional honeycomb structure in 650 DEG C of calcining 1h
ZnO nano material；Honeycomb size through detecting the three-dimensional honeycomb structure ZnO nano material that the embodiment obtains is about 90nm；Than
Surface area 265m2/g。
Embodiment 4:
A kind of controllable method for preparing of three-dimensional honeycomb structure ZnO nano material, comprising the following steps:
Step 1: pectin is dissolved in deionized water, it is configured to the pectin solution that concentration is 1mol/L；Transfer them to hydro-thermal
In reaction kettle, 6h is reacted at 180 DEG C；Through washing, 60 DEG C of drying after cooling, the unicity of particle size about 85nm is made, divides
Dissipate the good nano carbon microsphere of property；
Step 2: the nano carbon microsphere of step 1 is impregnated in deionized water in the ratio that solid-liquid mass ratio is 1:50, system
Obtain coating reaction bottom liquid；The pH value of coating reaction bottom liquid is adjusted to 6 with hydrochloric acid；
Step 3: respectively by concentration be 0.5mol/L liquor zinci chloridi 100mL and mass concentration be 10% bicarbonate
Ammonium salt solution is slowly dropped into the coating reaction bottom liquid of step 2 with the speed ratio of 5:1 simultaneously, and control pH value in reaction is 6 and reaction temperature
Degree is 35 DEG C, and is stirred to coating reaction bottom liquid, and reaction is completed and after centrifugation, washing, 60 DEG C of drying, and Zn is made
(OH)2/ carbon ball composite material；The mass volume ratio of nano carbon microsphere and zinc solution in the liquid of the coating reaction bottom is 1:120；
The rate of addition of the acetic acid zinc solution is 3mL/min；
Step 4: by the Zn (OH) of step 32/ carbon ball composite material obtains three-dimensional honeycomb structure in 650 DEG C of calcining 1h
ZnO nano material；Honeycomb size through detecting the three-dimensional honeycomb structure ZnO nano material that the embodiment obtains is about 85nm；Than
Surface area 323m2/g。
Embodiment 5:
A kind of controllable method for preparing of three-dimensional honeycomb structure ZnO nano material, comprising the following steps:
Step 1: deionized water is added in konjaku glucomannan, it is configured to the konjaku glucomannan that concentration is 0.2mol/L
Colloidal sol；It transfers them in hydrothermal reaction kettle, reacts 5h at 220 DEG C；Through washing, 60 DEG C of drying after cooling, it is big that partial size is made
The nano carbon microsphere of the unicity of small about 90nm, favorable dispersibility；
Step 2: the nano carbon microsphere of step 1 is impregnated in deionized water in the ratio that solid-liquid mass ratio is 1:40, system
Obtain coating reaction bottom liquid；The pH value of coating reaction bottom liquid is adjusted to 6.5 with hydrochloric acid；
Step 3: respectively by concentration be 0.5mol/L zinc nitrate solution 100mL and mass concentration be 10% urea it is molten
Liquid is slowly dropped into the coating reaction bottom liquid of step 2 with the speed ratio of 5:1 simultaneously, and control pH value in reaction is 6.5 and reaction temperature
It is 35 DEG C, and be stirred to coating reaction bottom liquid, reaction is completed and after centrifugation, washing, 60 DEG C of drying, is made Zn (OH)2/
Carbon ball composite material；The mass volume ratio of nano carbon microsphere and zinc solution in the liquid of the coating reaction bottom is 1:80；The second
The rate of addition of sour zinc solution is 5mL/min；
Step 4: by the Zn (OH) of step 32/ carbon ball composite material obtains three-dimensional honeycomb structure in 700 DEG C of calcining 2h
ZnO nano material；Honeycomb size through detecting the three-dimensional honeycomb structure ZnO nano material that the embodiment obtains is about 90nm；Than
Surface area 272m2/g。
Embodiment 6:
A kind of controllable method for preparing of three-dimensional honeycomb structure ZnO nano material, comprising the following steps:
Step 1: deionized water is added in maltose, it is configured to the maltose solution that concentration is 0.5mol/L；It is shifted
Into hydrothermal reaction kettle, 3h is reacted at 180 DEG C；Through washing, 60 DEG C of drying after cooling, the single of particle size about 85nm is made
The nano carbon microsphere of property, favorable dispersibility；
Step 2: the nano carbon microsphere of step 1 is impregnated in deionized water in the ratio that solid-liquid mass ratio is 1:20, system
Obtain coating reaction bottom liquid；The pH value of coating reaction bottom liquid is adjusted to 5.5 with sulfuric acid；
Step 3: respectively by concentration be 0.5mol/L solution of zinc sulfate 100mL and mass concentration be 10% ammonium carbonate
Solution is slowly dropped into the coating reaction bottom liquid of step 2 with the speed ratio of 4:1 simultaneously, and control pH value in reaction is 5.5 and reaction temperature
Degree is 40 DEG C, and is stirred to coating reaction bottom liquid, and reaction is completed and after centrifugation, washing, 60 DEG C of drying, and Zn is made
(OH)2/ carbon ball composite material；The mass volume ratio of nano carbon microsphere and zinc solution in the liquid of the coating reaction bottom is 1:80；
The rate of addition of the acetic acid zinc solution is 5mL/min；
Step 4: by the Zn (OH) of step 32/ carbon ball composite material obtains three-dimensional honeycomb structure in 650 DEG C of calcining 2h
ZnO nano material；Honeycomb size through detecting the three-dimensional honeycomb structure ZnO nano material that the embodiment obtains is about 85nm；Than
Surface area 332m2/g。
Embodiment 7:
In the step 3, during the reaction, apply ultrasound into coating reaction bottom liquid, while to coating reaction bottom liquid
In be passed through nitrogen；The flow velocity of the nitrogen is 200mL/min；The frequency of the ultrasound is 45KHz, and ultrasound uses intermitant irradiation,
Intermittent time when intermitant irradiation is 20s/10s, i.e. irradiation 20s, stops irradiation 10s, is repeated with this；
Remaining technological parameter and process with it is identical in embodiment 1；The three-dimensional honeycomb obtained through detecting the embodiment
The honeycomb size of structure ZnO nano material is about 70nm；Specific surface area 382m2/g。
Embodiment 8:
In the step 3, during the reaction, apply ultrasound into coating reaction bottom liquid, while to coating reaction bottom liquid
In be passed through nitrogen；The flow velocity of the nitrogen is 250mL/min；The frequency of the ultrasound is 40KHz, and ultrasound uses intermitant irradiation,
Intermittent time when intermitant irradiation is 15s/5s, i.e. irradiation 15s, stops irradiation 5s, is repeated with this；
Remaining technological parameter and process with it is identical in embodiment 3；The three-dimensional honeycomb obtained through detecting the embodiment
The honeycomb size of structure ZnO nano material is about 80nm；Specific surface area 315m2/g。
Embodiment 9:
In the step 1, before washing further include: the feed liquid after reaction is added in stainless steel spherical container, simultaneously
The ethyl alcohol of material liquid volume 1/3, sealing is added, and the spherical container after sealing is placed on four axis bevellers, opens the grinding of four axis
Instrument drives stainless steel spherical container randomly to rotate 60min；The feed inlet of the stainless steel spherical container is sealed by threaded cap,
Threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；The shaft revolving speed of the four axis beveller is 200rpm,
Stochastic transition frequency is 10s.
Remaining technological parameter and process with it is identical in embodiment 1；The three-dimensional honeycomb obtained through detecting the embodiment
The honeycomb size of structure ZnO nano material is about 65nm, and honeycomb is more uniform；Specific surface area 402m2/g。
Embodiment 10:
In the step 1, before washing further include: the feed liquid after reaction is added in stainless steel spherical container, simultaneously
The ethyl alcohol of material liquid volume 1/3, sealing is added, and the spherical container after sealing is placed on four axis bevellers, opens the grinding of four axis
Instrument drives stainless steel spherical container randomly to rotate 45min；The feed inlet of the stainless steel spherical container is sealed by threaded cap,
Threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；The shaft revolving speed of the four axis beveller is 150rpm,
Stochastic transition frequency is 20s.
Remaining technological parameter and process with it is identical in embodiment 3；The three-dimensional honeycomb obtained through detecting the embodiment
The honeycomb size of structure ZnO nano material is about 76nm, and honeycomb is more uniform；Specific surface area 395m2/g。
Embodiment 11:
Process is carried out the following processing to nano carbon microsphere obtained in the step 1: nano carbon microsphere is sent into atmos low-temperature
In plasma device, nano carbon microsphere is set to be in 40mm at the jet exit of atmos low-temperature plasma, in atmos low-temperature
Throughput in plasma device according to 15L/h is passed through gas, under atmospheric conditions, fills in atmos low-temperature plasma
Apply operating voltage on the high-field electrode and grounding electrode set, passes through the flowing gas into atmos low-temperature plasma device
Electric discharge generates plasma, forms plasma jet, controls the movement of the jet exit of atmos low-temperature plasma device
Speed makes plasma jet injection on nano carbon microsphere, handles 90min to nano carbon microsphere in 12mm/s；The operating voltage
It is provided using high-voltage ac power, the operating voltage is the alternating voltage of 100kV, frequency 250kHz；The gas is sky
The mixing of gas and ammonia；
Remaining technological parameter and process with it is identical in embodiment 1；The three-dimensional honeycomb obtained through detecting the embodiment
The honeycomb size of structure ZnO nano material is about 40nm, and honeycomb is more uniform；Specific surface area 580m2/g。
Embodiment 12:
Process is carried out the following processing to nano carbon microsphere obtained in the step 1: nano carbon microsphere is sent into atmos low-temperature
In plasma device, nano carbon microsphere is set to be in 30mm at the jet exit of atmos low-temperature plasma, in atmos low-temperature
Throughput in plasma device according to 12L/h is passed through gas, under atmospheric conditions, fills in atmos low-temperature plasma
Apply operating voltage on the high-field electrode and grounding electrode set, passes through the flowing gas into atmos low-temperature plasma device
Electric discharge generates plasma, forms plasma jet, controls the movement of the jet exit of atmos low-temperature plasma device
Speed makes plasma jet injection on nano carbon microsphere, handles 60min to nano carbon microsphere in 10mm/s；The operating voltage
It is provided using high-voltage ac power, the operating voltage is the alternating voltage of 100kV, frequency 250kHz；The gas is dilute
There is the mixing of gas/oxygen and ammonia；
Remaining technological parameter and process with it is identical in embodiment 3；The three-dimensional honeycomb obtained through detecting the embodiment
The honeycomb size of structure ZnO nano material is about 45nm, and honeycomb is more uniform；Specific surface area 565m2/g。
Embodiment 13:
The process calcined in the step 4 are as follows: by Zn (OH)2/ carbon ball composite material is added in rotary roasting furnace, with 5
DEG C/speed of min is heated to 100 DEG C, 30min is kept the temperature, is then heated to 500 DEG C with the speed of 1 DEG C/min, heat preservation
Then 60min is heated to 600 DEG C with the speed of 0.5 DEG C/min, keep the temperature 90min, obtain three-dimensional honeycomb structure ZnO nanometer
Material；The rotation speed of the rotary roasting furnace is 10r/min.
Remaining technological parameter and process with it is identical in embodiment 1；The three-dimensional honeycomb obtained through detecting the embodiment
The honeycomb size of structure ZnO nano material is about 70nm, and honeycomb is more uniform；Specific surface area 412m2/g。
Embodiment 14:
The process calcined in the step 4 are as follows: by Zn (OH)2/ carbon ball composite material is added in rotary roasting furnace, with 4
DEG C/speed of min is heated to 200 DEG C, 30min is kept the temperature, is then heated to 500 DEG C with the speed of 1 DEG C/min, heat preservation
Then 60min is heated to 650 DEG C with the speed of 1 DEG C/min, keep the temperature 90min, obtain three-dimensional honeycomb structure ZnO nanometer material
Material；The rotation speed of the rotary roasting furnace is 10r/min.
Remaining technological parameter and process with it is identical in embodiment 3；The three-dimensional honeycomb obtained through detecting the embodiment
The honeycomb size of structure ZnO nano material is about 75nm, and honeycomb is more uniform；Specific surface area 405m2/g。
Embodiment 15:
In the step 1, before washing further include: the feed liquid after reaction is added in stainless steel spherical container, simultaneously
The ethyl alcohol of material liquid volume 1/3, sealing is added, and the spherical container after sealing is placed on four axis bevellers, opens the grinding of four axis
Instrument drives stainless steel spherical container randomly to rotate 60min；The feed inlet of the stainless steel spherical container is sealed by threaded cap,
Threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；The shaft revolving speed of the four axis beveller is 200rpm,
Stochastic transition frequency is 10s.
Remaining technological parameter and process with it is identical in embodiment 11；The three-dimensional honeycomb obtained through detecting the embodiment
The honeycomb size of structure ZnO nano material is about 20nm, and honeycomb is more uniform；Specific surface area 850m2/g。
The three-dimensional honeycomb knot prepared in micron order ZnO, the nanoscale ZnO and the embodiment of the present invention 1 sold using market
Structure ZnO nano material carries out photocatalysis test, process are as follows: using three kinds of materials as photochemical catalyst, with time of 0.6mg/L
Methyl blue solution 250mL be degradation test solution, be separately added into 0.001g photochemical catalyst while stirring, under the irradiation of 100W mercury lamp into
The degradation of row room temperature, light source distance liquid level 20cm, interval 15min take a supernatant liquor, take altogether 6 times, and when 90min takes last
It is secondary；Its absorbance is measured using ultraviolet-visible photometer, is calculate by the following formula degradation rate:
η=(A0-Ax)/A0× 100%
A0For the absorbance value of methylene blue before illumination degrading；AxFor the absorbance value of methylene blue after illumination degrading；As a result
As shown in figure 4, degradation effect tends towards stability in 90min；It can be received with three-dimensional honeycomb structure ZnO prepared by the embodiment of the present invention 1
Rice material has excellent photocatalysis performance；Under ultraviolet light 90min irradiation, to the methylene blue solution Central Asia of 0.6mg/L
The degradation rate of methyl blue reaches 95%, and the corresponding degradation rate than traditional micron order ZnO (about 5 μm of partial size) improves about 108%, than receiving
The corresponding degradation rate of meter level ZnO (partial size about 60mm) improves about 31%.
Photocatalysis test, process are carried out using the three-dimensional honeycomb structure ZnO nano material prepared in embodiment 1~15
Are as follows: the three-dimensional honeycomb structure ZnO nano material prepared respectively using in embodiment 1~15 is as photochemical catalyst, with time of 0.6mg/L
Methyl blue solution 250mL be degradation test solution, be separately added into 0.001g photochemical catalyst while stirring, under the irradiation of 100W mercury lamp into
The degradation of row room temperature, when 90min, take supernatant liquor；Its absorbance is measured using ultraviolet-visible photometer, is calculate by the following formula drop
Solution rate:
η=(A0-Ax)/A0× 100%
A0For the absorbance value of methylene blue before illumination degrading；AxFor the absorbance value of methylene blue after illumination degrading；It is dropped
The results are shown in Table 1 for solution rate；
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Degradation rate | 95% | 97.5% | 92.5% | 95.8% | 92.3% | 96.2% | 97% | 95.6% |
| Embodiment | 9 | 10 | 11 | 12 | 13 | 14 | 15 | |
| Degradation rate | 97.3% | 96.5% | 98.8% | 98% | 97.7% | 96.8% | 99.8% |
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (4)
1. a kind of controllable method for preparing of three-dimensional honeycomb structure ZnO nano material, which comprises the following steps:
Step 1: carbon source material is dissolved in deionized water, it is configured to the carbon source material solution that concentration is 0.1~1mol/L；By its
It is transferred in hydrothermal reaction kettle, 1~6h is reacted at 140~240 DEG C；Through washing, 60 DEG C of drying after cooling, nano-sized carbon is obtained
Ball；The carbon source material is glucose, fructose, sucrose, maltose, pectin, starch, cellulose, appointing in konjaku glucomannan
It anticipates one kind；
Step 2: the nano carbon microsphere of step 1 is impregnated in deionized water in the ratio that solid-liquid mass ratio is 1:50~1:20,
Coating reaction bottom liquid is made；The pH value of coating reaction bottom liquid is adjusted with acid to 4~7；The acid is acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid
In any one；
Step 3: respectively by concentration be 0.1~1mol/L zinc solution and mass concentration be 5~10% aqueous slkali simultaneously with
The speed ratio of 2:1~5:1 is slowly dropped into the coating reaction bottom liquid of step 2, and control pH value in reaction is 4~7 and reaction temperature is
20~40 DEG C, and coating reaction bottom liquid is stirred, reaction is completed and after centrifugation, washing, 50~70 DEG C of drying, and Zn is made
(OH)2/ carbon ball composite material；The mass volume ratio of nano carbon microsphere and zinc solution in the liquid of the coating reaction bottom be 1:80~
120；The zinc solution is acetic acid zinc solution, zinc nitrate solution, liquor zinci chloridi, zinc sulfate, any in oxalic acid zinc solution
It is a kind of；The aqueous slkali is weak aqua ammonia, urea liquid, sodium carbonate liquor, sodium bicarbonate solution, ammonium bicarbonate soln, ammonium carbonate
Any one in solution, sodium hydroxide solution；
Step 4: by the Zn (OH) of step 32/ carbon ball composite material obtains three-dimensional honeycomb knot in 550~750 DEG C of 1~3h of calcining
Structure ZnO nano material；
Process is carried out the following processing to nano carbon microsphere obtained in the step 1: by nano carbon microsphere be sent into atmos low-temperature etc. from
In daughter device, nano carbon microsphere is set to be in 20~60mm at the jet exit of atmos low-temperature plasma, in atmos low-temperature
Throughput in plasma device according to 5~15L/h is passed through gas, applies operating voltage, forms plasma jet, control
The movement speed of the jet exit of atmos low-temperature plasma device makes plasma jet injection in receiving in 5~15mm/s
In rice carbon ball, 60~90min is handled to nano carbon microsphere；The operating voltage is provided using high-voltage ac power, the work electricity
Pressure is the alternating voltage of 35~100kV, and frequency is 100~300kHz；The gas be air, rare gas/oxygen, oxygen,
The mixing of one or more of nitrogen, ammonia.
2. the controllable method for preparing of three-dimensional honeycomb structure ZnO nano material as described in claim 1, which is characterized in that described
In step 3, during the reaction, apply ultrasound into coating reaction bottom liquid, while being passed through nitrogen into coating reaction bottom liquid；
The flow velocity of the nitrogen is 150~250mL/min；The frequency of the ultrasound is 30~45KHz, and ultrasound uses intermitant irradiation,
The intermittent time having a rest when irradiating is 15~20s/5~10s.
3. the controllable method for preparing of three-dimensional honeycomb structure ZnO nano material as described in claim 1, which is characterized in that described
In step 1, before washing further include: the feed liquid after reaction is added in stainless steel spherical container, while material liquid volume is added
1/3 ethyl alcohol, sealing, and the spherical container after sealing is placed on four axis bevellers, four axis bevellers are opened, stainless steel is driven
Spherical container randomly rotates 30~60min；The feed inlet of the stainless steel spherical container is sealed by threaded cap, threaded cap sealing
It is flushed after connection with the surface of stainless steel spherical container；The shaft revolving speed of the four axis beveller is 150~200rpm, random to turn
Frequency is 10~20s.
4. the controllable method for preparing of three-dimensional honeycomb structure ZnO nano material as described in claim 1, which is characterized in that described
The process calcined in step 4 are as follows: by Zn (OH)2/ carbon ball composite material is added in rotary roasting furnace, with the speed of 3~5 DEG C/min
Degree is heated to 100~300 DEG C, keeps the temperature 10~30min, then 400 are heated to the speed of 1~2.5 DEG C/min~
500 DEG C, 30~60min is kept the temperature, is then heated to 550~750 DEG C with the speed of 0.5~1 DEG C/min, heat preservation 60~
90min obtains three-dimensional honeycomb structure ZnO nano material；The rotation speed of the rotary roasting furnace is 5~10r/min.
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