CN106311143B - A kind of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material and the preparation method and application thereof - Google Patents
A kind of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material and the preparation method and application thereof Download PDFInfo
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- CN106311143B CN106311143B CN201610813681.2A CN201610813681A CN106311143B CN 106311143 B CN106311143 B CN 106311143B CN 201610813681 A CN201610813681 A CN 201610813681A CN 106311143 B CN106311143 B CN 106311143B
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
Abstract
The invention discloses a kind of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon materials and the preparation method and application thereof.It is freeze-dried after silkworm excrement first to be mixed to swelling with water; silkworm excrement after freeze-drying is prepared into carbonization silkworm excrement under protective gas again; to be carbonized silkworm excrement and KOH mixing again; activation reaming reaction is carried out in protective gas; then high-ratio surface silkworm excrement base micropore carbon material is obtained after cleaning, be centrifuged and drying again, then is passed through N2Atmosphere prepares high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material in plasma reactor, which can be applied to pesticide and delay controlled release aspect.The present invention is carbonized and is activated to silkworm excrement using protection gas bar part at high temperature; the modification of N doping surfaces is carried out to the material by way of plasma modification again; obtained Carbon Materials specific surface area with higher and controllable polar group containing N, can there is higher adsorption capacity and preferable slow-releasing and controlled-releasing action to pesticide.
Description
Technical field
The invention belongs to Carbon Materials technical fields, and in particular to N doping surfaces modify silkworm excrement base micropore carbon material and its system
Preparation Method and application.
Background technique
Pesticide can efficiently control the harm of disease, worm, grass and other harmful organisms to crops, it is as chemical prevention
Important means, play irreplaceable role in agricultural production.However, pesticide only a small amount of in specific time can arrive
Up to crop target site, and most of pesticide is directly released into natural environment and causes pesticide utilization efficiency low.This part is not
The pesticide for playing drug effect can cause Practice for Pesticide Residue in Agricultural Products exceeded, injury and environmental pollution to non-target organism etc. many negative
Face problem.The utilization efficiency and Targeting delivery function for how effectively improving pesticide are urgently to be resolved main of current pesticide field
One of problem.
Slow controlled-release technology is that one kind can be such that pesticide activity component slowly releases within given time by physically or chemically means
It is put in target site, and drug concentration is made to maintain the novel medicine feeding technology of effective concentration or more in a long time.Biology is more
Hole charcoal is that have one of the material preferably adsorbed, main waste silkworm excrement of the silkworm excrement base charcoal in silkworm industry,
Often arbitrarily abandoning in rural area leads to environmental pollution, silkworm excrement known to from Electron microscope from natural three-dimensional drape structure and
Phosphorus content is high, can obtain high-ratio surface multiporous biological charcoal, and its surface N (O) also rich in through high temperature cabonization and activation
Group can promote its slow controlled release ability by modification.
Summary of the invention
It modifies silkworm excrement base micropore carbon material and preparation method thereof the invention proposes a kind of high-ratio surface N doping surfaces and answers
With.The present invention is carbonized again after first carrying out swelling expanding treatment to silkworm excrement, then at high temperature using protection gas bar part to silkworm after freeze-drying
Sand is activated, then carries out the modification of N doping surfaces, obtained raw material of wood-charcoal to the material by way of plasma modification
Expect specific surface area with higher and controllable polar group containing N, can there is higher adsorption capacity and preferable slow control to pesticide
Release effect.
The purpose of the present invention is achieved through the following technical solutions:
High-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material of the invention is three dimensional pore structures,
Langmuir specific surface area is 1000-1300m2/ g, total pore volume is in 0.4-0.6cm3/ g, wherein micropore specific area and Kong Rongzhan
To 80% or more of total specific surface area and Kong Rong.
High-ratio surface N doping surfaces of the invention modify silkworm excrement base micropore carbon preparation method for material, include the following steps:
(1) Faeces bombycis is freeze-dried after mixing swelling with water, then by silkworm excrement after freeze-drying in N2, in the protective gas such as Ar gas
Preparation carbonization silkworm excrement is reacted by high temperature cabonization；
(2) will carbonization silkworm excrement and KOH mix, carried out in protective gas activation reaming reaction, then clean again, be centrifuged with
And high-ratio surface silkworm excrement base micropore carbon material is obtained after drying.Cleaning rinses 3 times to obtain high-ratio surface silkworm excrement using dilute hydrochloric acid and water
Base micropore carbon material.
(3) by high-ratio surface silkworm excrement base micropore carbon material and in N2Plasma reactor carry out table is put under atmosphere protection
Face is modified, 20~30V of input voltage of plasma device, 10~20min of modification time；It is modified to wash with water drying and obtain height
Specific surface N doping surfaces modify silkworm excrement base micropore carbon material.
As the further preferred of scheme, step (1) Faeces bombycis is 1:100~200, mixing temperature with water mixing plastid ratio
It is 30~50 DEG C, incorporation time is 0.5~3h.Freezing dry process is first 2~4h of precooling at -25 ° DEG C~-20C, then
It is cooled to -60 DEG C~-40 DEG C 24~72h of freeze-drying.
As the further preferred of scheme, the carburizing temperature of silkworm excrement is at 700-1000 DEG C, reaction after being lyophilized in step (1)
Between 2~4h.
As the further preferred of scheme, the mass ratio that KOH is mixed with carbonization silkworm excrement in the step (2) is (6-1): 1.
As the further preferred of scheme, the reaming reaction temperature is 650~950 DEG C, and the reaction time is 0.5~5h.
Optimum reaction condition is that reaming reaction temperature is 750~850 DEG C, and the reaction time is 2~3h, and activation temperature has to be lower than carbon
Change temperature, excessively high temperature is destroyed again when guaranteeing that the carbon skeleton pattern formed in carbonisation will not be activated.
In terms of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material of the invention can be applicable to medicine sustained and controlled release,
In terms of especially pesticide delays controlled release.
Product of the present invention, which is applied, delays controlled release field in pesticide, adsorbs anabasine pesticide Diacloden, absorption using the material
Load capacity can reach 500mg/g or more, and can prepare and delay controlled release farm chemical carrier within the scope of 15~60 days effective time of sustained release (to release
90% Diacloden of total amount is put as endpoint calculation).
The principle of the invention: limited swelling work can occur in aqueous solution for the special macromolecular structure as possessed by silkworm excrement
With volume will increase 1~20 times after swelling, silkworm excrement after swelling is freeze-dried by substep, freezing pretreatment can make silkworm excrement
Fluffy macromolecular structure when keeping being swollen, then freeze-drying ensure that the abundant drying of silkworm excrement, and further consolidate its structure, can prolong
Long silkworm excrement carbon skeleton improves the specific surface area and porosity of silkworm excrement base Carbon Materials after carbonization-activation.Pass through the side of plasma modification
Formula is in N2The modification of N doping surfaces is carried out to the material under atmospheric condition, C, O, H atom and the plasma of material surface can be made
N atom under state combines, and in the material surface formation-CN ,-NO3With-NH2Equal nitrogen-containing groups.In conventional pesticide molecule
Mostly containing polar group (carboxyl, carbonyl, sulfur-bearing and containing cl radical etc.), and this segment polarity group is also the master in pesticide
Active part is wanted, these polar groups can be in conjunction with the nitrogen-containing group in silkworm excrement.Just by control plasma modification condition
The nitrogen-containing group quantity of adjustable silkworm excrement base charcoal material surface, and then the adsorption capacity of pesticide and Carbon Materials can be regulated and controled, reach
To the slow-releasing and controlled-releasing action of pesticide.
Plasma just refers to ionized gas, it is the molecular collection of the grains such as electronics, ion, atom, molecule or free radical
Zoarium, these are all as lively as a cricket reactive species.Particle combines bond energy between capable of destroying original material molecule in plasma, and
Molecule and plasma intermediate ion is set in material to be combined into new chemical bond, and since its energy is penetrated far below high-energy radioactive
Line, thus plasma pertains only to the surface of material, does not influence the bulk properties of material, and plasma modification has efficient, ring
The advantages that protecting, be easily controllable, easy to operate.
Compared with prior art, the present invention is advantageous in that:
1. the raw materials used in the present invention silkworm excrement has native three dimensional pleated structure and contains a large amount of carboxyls, hydroxyl and amino base
Group can form high-ratio surface micropore knot on carbonization silkworm excrement surface using KOH high-temperature activation carbonization silkworm excrement under protective gas
Structure obtains the relatively high-adsorption-capacity to pesticide by the microcellular structure of high-ratio surface, and carries out under the voltage conditions of 20~30V
It is modified, effectively increase reaction speed of the plasma nitrogen-atoms on silkworm excrement base Carbon Materials.
2. by silkworm excrement swelling action can in the case where not changing silkworm excrement polymer configuration by silkworm excrement volume increase 1~
20 times, its internal structure is fixed by silkworm excrement after swelling by way of freeze-drying, silkworm excrement base after carbonization-activation can be improved
The porosity and specific surface area of Carbon Materials.
3. being modified by plasma mode to silkworm excrement base Carbon Materials, in N2Under atmosphere by plasma N atom with
Material surface C, O, H atom combine, formation-CN ,-NO3With-NH2Equal nitrogen-containing groups.The reaction and tradition N doping way (triazine
Class compound, urea etc.) compared to having a clear superiority: (1) without containing other nitrogenous compounds only use N2Doping, reduces other members
Influence of the element to reaction system；(2) reaction time short (within 30min), be added without other reaction dissolvents eliminate reaction after from
The heart, filtering and etc..
4. by the quantity of the factor controllings silkworm excrement surface nitrogen-containing groups such as plasma modification condition, since nitrogen-containing group can be right
Adsorption capacity between pesticide and material has an important influence on, thus by the controllable silkworm excrement base Carbon Materials of plasma modification condition with
Adsorption capacity between pesticide molecule achievees the purpose that delay controlled release to pesticide.
5. activation temperature used in the present invention will be lower than carburizing temperature, to guarantee to silkworm excrement base charcoal material surface N (O) group number
The control of amount and the guarantee of silkworm excrement base Carbon Materials support frame stability.
6. material prepared by the present invention is for adsorbing anabasine pesticide Diacloden, adsorbance can reach 500mg/g
More than, sustained-release pesticides carrier of the slow-release time within the scope of 15~60 days can be prepared (to discharge always by regulating and controlling carburizing temperature
90% Diacloden is measured as endpoint calculation).
Detailed description of the invention
Fig. 1 is that Faeces bombycis is sliced electron-microscope scanning figure.
Fig. 2 is silkworm excrement slice electron-microscope scanning figure after swelling freeze-drying.
Fig. 3 is silkworm excrement inner surface electron-microscope scanning figure after swelling freeze-drying.
Fig. 4 is that 1 high-ratio surface N doping surfaces of embodiment modify silkworm excrement base micropore carbon material electron-microscope scanning figure.
Fig. 5 difference slow-release material load capacity curve.
Fig. 6 difference slow-release material is sustained release profiles.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the range of embodiment statement.
Embodiment 1
A kind of preparation method of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material, includes the following steps,
It (1) is that 1:100 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 3.0h at 30 DEG C
Silkworm excrement is pulled out and is freeze-dried, first pre-processes 4h in -20 DEG C of freezings, then reduces temperature to -60 DEG C of freeze-dryings and is lyophilized for 24 hours
Silkworm excrement afterwards.
In N2Silkworm excrement is raised to 700 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in atmosphere, and protects at 700 DEG C
Room temperature, preparation carbonization silkworm excrement are cooled to after holding 3h or more.
(2) carbonization silkworm excrement and KOH are mixed with mass ratio 1:1, in N2It is raised in atmosphere with the heating rate of 5 DEG C/min
650 DEG C, and keep 5.0h to carry out reaming reaction at 650 DEG C and obtained solid is dissolved in 1mol/L to be cooled to room temperature naturally
HCl in cleaning dissolution KOH, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface silkworm excrement base micropore carbon material.
(3) 1.0g high-ratio surface silkworm excrement base micropore carbon material is put into plasma reactor, is passed through N2As modification
Gas, plasma reactor input voltage 20V, modification time 20min, it is modified cleared up 3 times with deionized water after low temperature it is dry
It is dry to obtain high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material.
Embodiment 2
It (1) is that 1:120 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 2.5h at 35 DEG C
Silkworm excrement is pulled out and is freeze-dried, first pre-processes 3h in -20 DEG C of freezings, then reduces temperature extremely -55 DEG C of freeze-drying 36h and is lyophilized
Silkworm excrement afterwards.
Silkworm excrement is raised to 800 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in an ar atmosphere, and protects at 800 DEG C
Room temperature, preparation carbonization silkworm excrement are cooled to after holding 2.5h or more.
(2) carbonization silkworm excrement and KOH are mixed with mass ratio 1:2, in N2It is raised in atmosphere with the heating rate of 5 DEG C/min
750 DEG C, and keep 4.0h to carry out reaming reaction at 750 DEG C and obtained solid is dissolved in 1mol/L to be cooled to room temperature naturally
HCl in cleaning dissolution KOH, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface silkworm excrement base micropore carbon material.
(3) 1.0g high-ratio surface silkworm excrement base micropore carbon material is put into plasma reactor, is passed through N2As modification
Gas, plasma reactor input voltage 22V, modification time 18min, it is modified cleared up 3 times with deionized water after low temperature it is dry
It is dry to obtain high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material.
Embodiment 3
It (1) is that 1:140 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 2.0h at 40 DEG C
Silkworm excrement is pulled out and is freeze-dried, first pre-processes 2h in -25 DEG C of freezings, then reduces temperature extremely -50 DEG C of freeze-drying 48h and is lyophilized
Silkworm excrement afterwards.
In N2Silkworm excrement is raised to 850 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in atmosphere, and protects at 850 DEG C
Room temperature, preparation carbonization silkworm excrement are cooled to after holding 2.0h or more.
(2) carbonization silkworm excrement and KOH are mixed with mass ratio 1:3, in N2It is raised in atmosphere with the heating rate of 5 DEG C/min
800 DEG C, and keep 3.0h to carry out reaming reaction at 800 DEG C and obtained solid is dissolved in 1mol/L to be cooled to room temperature naturally
HCl in cleaning dissolution KOH, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface silkworm excrement base micropore carbon material.
(3) 1.0g high-ratio surface silkworm excrement base micropore carbon material is put into plasma reactor, is passed through N2As modification
Gas, plasma reactor input voltage 24V, modification time 16min, it is modified cleared up 3 times with deionized water after low temperature it is dry
It is dry to obtain high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material.
Embodiment 4
It (1) is that 1:160 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 1.5h at 40 DEG C
Silkworm excrement is pulled out and is freeze-dried, first pre-processes 2.5h in -25 DEG C of freezings, then reduces temperature extremely -40 DEG C of freeze-drying 72h and is frozen
Silkworm excrement after dry.
Silkworm excrement is raised to 900 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in an ar atmosphere, and protects at 900 DEG C
Room temperature, preparation carbonization silkworm excrement are cooled to after holding 1.5h or more.
(2) carbonization silkworm excrement and KOH are mixed with mass ratio 1:4, in N2It is raised in atmosphere with the heating rate of 5 DEG C/min
850 DEG C, and keep 2.0h to carry out reaming reaction at 850 DEG C and obtained solid is dissolved in 1mol/L to be cooled to room temperature naturally
HCl in cleaning dissolution KOH, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface silkworm excrement base micropore carbon material.
(3) 1.0g high-ratio surface silkworm excrement base micropore carbon material is put into plasma reactor, is passed through N2As modification
Gas, plasma reactor input voltage 26V, modification time 14min, it is modified cleared up 3 times with deionized water after low temperature it is dry
It is dry to obtain high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material.
Embodiment 5
It (1) is that 1:180 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 1.0h at 45 DEG C
Silkworm excrement is pulled out and is freeze-dried, first pre-processes 4h in -20 DEG C of freezings, then reduces temperature extremely -45 DEG C of freeze-drying 60h and is lyophilized
Silkworm excrement afterwards.
In N2Silkworm excrement is raised to 950 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in atmosphere, and protects at 950 DEG C
Room temperature, preparation carbonization silkworm excrement are cooled to after holding 1.5h or more.
(2) carbonization silkworm excrement and KOH are mixed with mass ratio 1:5, in N2It is raised in atmosphere with the heating rate of 5 DEG C/min
900 DEG C, and keep 1.0h to carry out reaming reaction at 900 DEG C and obtained solid is dissolved in 1mol/L to be cooled to room temperature naturally
HCl in cleaning dissolution KOH, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface silkworm excrement base micropore carbon material.
(3) 1.0g high-ratio surface silkworm excrement base micropore carbon material is put into plasma reactor, is passed through N2As modification
Gas, plasma reactor input voltage 28V, modification time 12min, it is modified cleared up 3 times with deionized water after low temperature it is dry
It is dry to obtain high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material.
Embodiment 6
It (1) is that 1:200 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 0.5h at 50 DEG C
Silkworm excrement is pulled out and is freeze-dried, first pre-processes 4h in -20 DEG C of freezings, then reduces temperature extremely -40 DEG C of freeze-drying 72h and is lyophilized
Silkworm excrement afterwards.
Silkworm excrement is raised to 1000 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in an ar atmosphere, and at 1000 DEG C
Room temperature, preparation carbonization silkworm excrement are cooled to after keeping 1.5h or more.
(2) carbonization silkworm excrement and KOH are mixed with mass ratio 1:6, in N2It is raised in atmosphere with the heating rate of 5 DEG C/min
950 DEG C, and keep 0.5h to carry out reaming reaction at 950 DEG C and obtained solid is dissolved in 1mol/L to be cooled to room temperature naturally
HCl in cleaning dissolution KOH, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface silkworm excrement base micropore carbon material.
(3) 1.0g high-ratio surface silkworm excrement base micropore carbon material is put into plasma reactor, is passed through N2As modification
Gas, plasma reactor input voltage 30V, modification time 10min, it is modified cleared up 3 times with deionized water after low temperature it is dry
It is dry to obtain high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material.
Material properties test:
(1) electron microscope of Carbon Materials
Using Japanese Hitachi S-3400N type low power scanning electron microscope to silkworm after Faeces bombycis slice, swelling freeze-drying
High-ratio surface N doping surfaces obtained by silkworm excrement inner surface and the embodiment of the present invention 1 modify silkworm excrement base after sand slice, swelling freeze-drying
Micropore carbon material carries out the characterization of material surface pattern, as shown in Figure 1, Figure 2, Figure 3, Figure 4.
By Fig. 1 and Fig. 2 comparison it is found that silkworm excrement volume becomes larger after swelling and internal layer generates a large amount of pore structures.Fig. 3
It is silkworm excrement inner surface electron-microscope scanning figure after being swollen, embodies silkworm excrement tridimensional network.Fig. 4 is that high-ratio surface N doping surfaces are repaired
Adorn silkworm excrement base micropore carbon material electron-microscope scanning figure, it can be seen that the silkworm excrement base Carbon Materials after plasma modification can form more
Pore structure.
(2) pore structure study of material
Use Micro company of the U.S. produce 3-Flex specific surface pore-size distribution instrument to prepared by the present invention not to be swollen
Silkworm excrement is that raw material prepares silkworm excrement porous carbon material (according to 5 activation condition of embodiment), Gao Bibiao after processing silkworm excrement and swelling treatment
N doping surfaces modification silkworm excrement base micropore carbon material pore structure in face is measured, and the results are shown in Table 1.
The specific surface area and pore-size distribution of 1. silkworm excrement base micropore carbon material of table.
Smicro, VtAnd VmicroRespectively indicate specific surface area provided by micropore, Kong Rong provided by total pore volume and micropore.
According to 1 column data of table it is found that silkworm excrement base micropore carbon material Langmuir specific surface prepared by six kinds of embodiments
Product is in 1000~1300m2/ g, total pore volume is about in 0.4-0.6cm3/ g, wherein micropore specific area and Kong Rong account for total specific surface area
With 80% or more of Kong Rong.Silkworm excrement porous carbon material is prepared with silkworm excrement after non-swelling treatment silkworm excrement and swelling treatment respectively, is compared
Surface area and porosity have significant difference, and the specific surface area and porosity for not being swollen silkworm excrement base Carbon Materials is only silkworm excrement base after being swollen
60% or so of Carbon Materials.By the ratio table for the silkworm excrement base micropore carbon material that the N doping surfaces that plasma modification obtains are modified
The data such as area and hole appearance illustrate that plasma modification can be to silkworm excrement base with to there is slightly decline (about 10% or so) before modified
Microporous Carbon surface pore structure has some effects.This explanation, in the embodiment of the present invention coverage area, prepares obtained silkworm
Husky base micropore carbon material is a kind of micropore carbon material with high specific surface area.
(3) different silkworm excrement base Carbon Materials and Faeces bombycis constituent content and product yield analysis
Using Japanese Hitachi S-3400N type low power scanning electron microscope energy spectrum analysis, to Faeces bombycis, unmodified silkworm
The modification silkworm excrement base micropore carbon material of high-ratio surface N doping surfaces obtained by the husky, embodiment of the present invention 1~6 carries out C, N, O element
Constituent analysis and product yield are more as shown in table 2.
The different silkworm excrement base Carbon Materials of table 2 and Faeces bombycis constituent content and product yield analysis
| Sample | C element (%) | N element (%) | O element (%) | Product yield (%) |
| Silkworm feculae | 71.82 | 3.03 | 21.86 | - |
| Unmodified silkworm excrement base Carbon Materials | 87.45 | 8.04 | 3.75 | 17.25 |
| 1 material of case study on implementation | 87.45 | 8.04 | 3.75 | 17.71 |
| 2 material of case study on implementation | 85.31 | 8.83 | 4.03 | 18.43 |
| 3 material of case study on implementation | 84.45 | 9.23 | 3.78 | 18.60 |
| 4 material of case study on implementation | 83.78 | 10.18 | 4.13 | 19.73 |
| 5 material of case study on implementation | 83.99 | 10.79 | 3.87 | 20.47 |
| 6 material of case study on implementation | 83.27 | 11.58 | 4.04 | 21.67 |
From 2 data of table it is found that with case 1~6 plasma modified condition voltage and action time increase N element
Content is continuously increased (i.e. nitrogen-containing group quantity is continuously increased) and product yield is continuously improved.
(4) silkworm excrement base micropore carbon material sustained release performance is analyzed
Pesticide thiophene is carried out to high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material prepared by case study on implementation 1,3,5
Worm piperazine absorption carriage amount and sustained release tracing analysis, wherein the adsorption conditions of Carbon Materials are that 50mg slow-release material is put into 50mL 0.8g/
Absorption is vibrated in L Diacloden solution, 30 DEG C of bath temperature, vibrates 200 revs/min of revolving speed；The sustained release condition of Carbon Materials is 50mg
Slow-release material is put into 120mL deionized water after absorption, is changed water 100mL daily, 30 DEG C of bath temperature, is vibrated 200 revs/min of revolving speed
Clock, experimental result difference are as shown in Figure 5, Figure 6.From figure 5 it can be seen that 3 kinds of slow-release materials are after absorption Diacloden 48 hours
Load capacity all reaches between 500~560mg/g, and does not have difference between three kinds of materials, illustrates that such material is having
Similar adsorption effect is able to maintain while there are different slow release effects.From fig. 6, it can be seen that respectively at 15 days, 30 days and 60 days
Release process (using 90% Diacloden of total volume as endpoint calculation) is completed in left and right, is able to satisfy wanting for different times pesticide slow-release
It asks.
The above embodiment of the present invention is only intended to clearly illustrate examples made by the present invention, and is not to of the invention
The restriction of embodiment.For those of ordinary skill in the art, other can also be made on the basis of the above description
Various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., the protection scope of the claims in the present invention should be included in
Within.
Claims (7)
1. a kind of application of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material, it is characterised in that: it is in the slow control of pesticide
Release the utilization of aspect；The material is three dimensional pore structures, and Langmuir specific surface area is 1000 ~ 1300 m2/ g, total pore volume are
0.4-0.6cm3/ g, wherein micropore specific area and Kong Rong account for 80% or more of total specific surface area and Kong Rong；Preparation method packet
Include following steps,
(1) Faeces bombycis is freeze-dried after mixing swelling with water, then silkworm excrement after freeze-drying is anti-by high temperature cabonization in protective gas
Carbonization silkworm excrement should be prepared；
(2) will carbonization silkworm excrement and KOH mix, carried out in protective gas activation reaming reaction, then clean again, be centrifuged and
Silkworm excrement base micropore carbon material is obtained after drying；
(3) by silkworm excrement base micropore carbon material in N2It is put into plasma reactor under atmosphere protection, in 20 ~ 30 V of input voltage
Under conditions of modified, 10 ~ 20 min of modification time that carries out surface；Modified to wash with water, drying can be obtained high-ratio surface N and mix
Miscellaneous surface modification silkworm excrement base micropore carbon material.
2. the application of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material according to claim 1, feature exist
In: silkworm excrement is 1:100 ~ 200 with water mixing plastid ratio in the step (1), and mixing temperature is 30 ~ 50 oC, and incorporation time is
0.5~3 h。
3. the application of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material according to claim 1, feature exist
In: freezing dry process is first 2 ~ 4h of precooling at -25 o C ~ -20oC in the step (1), is then cooled to -60 o
24 ~ 72h is lyophilized in the oC of C ~ -40.
4. the preparation of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material according to claim 1, feature exist
In: the carburizing temperature of silkworm excrement is in 700-1000 oC, 2 ~ 4 h of reaction time after being lyophilized in step (1).
5. the application of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material according to claim 1, feature exist
In: the mass ratio that KOH is mixed with carbonization silkworm excrement in the step (2) is 6 ~ 1:1.
6. the application of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material according to claim 1, feature exist
In: activation reaming reaction temperature is 650 ~ 950 oC in the step (2), and the reaction time is 0.5 ~ 5 h.
7. the application of high-ratio surface N doping surfaces modification silkworm excrement base micropore carbon material according to claim 1, feature exist
In: activation reaming reaction temperature has to be lower than carburizing temperature in step (1) in the step (2).
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