CN106179229B - A kind of high-ratio surface basic anhydride surface modification silkworm excrement base micropore carbon material and the preparation method and application thereof - Google Patents
A kind of high-ratio surface basic anhydride surface modification silkworm excrement base micropore carbon material and the preparation method and application thereof Download PDFInfo
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- CN106179229B CN106179229B CN201610812098.XA CN201610812098A CN106179229B CN 106179229 B CN106179229 B CN 106179229B CN 201610812098 A CN201610812098 A CN 201610812098A CN 106179229 B CN106179229 B CN 106179229B
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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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- 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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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Abstract
The invention discloses a kind of high-ratio surface basic anhydride surface modification silkworm excrement base micropore carbon materials and the preparation method and application thereof.It is freeze-dried after silkworm excrement is mixed swelling with water, silkworm excrement after freeze-drying is prepared into carbonization silkworm excrement under protective gas；To be carbonized silkworm excrement and KOH mixing; 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; centrifugation, drying, are passed through oxygen and prepare plasma modification basic anhydride surface modification silkworm excrement base micropore carbon material after being again stirred metal salt solution and the material.The material is applied to pesticide and delays controlled release aspect.The present invention is carbonized and is activated to silkworm excrement using protection gas bar part at high temperature; basic anhydride surface modification is carried out by way of infusion process and plasma modification; obtained Carbon Materials specific surface area with higher and basic sorbent site, have 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 basic surface modifies silkworm excrement base micropore carbon material and its 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, by the way that its slow controlled release ability can be promoted to its modification.
Summary of the invention
The object of the present invention is to provide a kind of high-ratio surface basic anhydride surface modification silkworm excrement base micropore carbon material and its
Preparation method and application.The present invention is carbonized again after first carrying out swelling expanding treatment to silkworm excrement, then is protected in high temperature using inert gas
Shield is activated silkworm excrement after freeze-drying, then by metal salt solution dipping, drying and plasma surface modification, acquired
Carbon Materials specific surface area with higher and basic sorbent site, can have higher adsorption capacity and preferably slow controlled release to pesticide
Effect.
The purpose of the present invention is achieved through the following technical solutions:
High-ratio surface basic anhydride surface 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 silkworm excrement base Microporous Carbon of the invention prepares the preparation method of material, includes 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 Gao Bibiao using dilute hydrochloric acid and deionized water
Face silkworm excrement base micropore carbon material；
(3) by high-ratio surface silkworm excrement base micropore carbon material and metal salt solution, (cation is Fe3+、Cu2+、Ag+Deng) oscillation
Drying, then O are centrifuged after mixing2It is modified that plasma reactor progress surface is put under atmosphere, the input voltage of plasma device
20~30V, 10~20min of modification time；It is modified to obtain high-ratio surface basic anhydride surface with deionized water cleaning, drying
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.
As the further preferred of scheme, the feed liquid of silkworm excrement base micropore carbon material and metal salt solution in the step (2)
Than for 1:100~150；Cation is Fe in metal salt solution3+、Cu2+、Ag+Metal salt solution, concentration is in 0.1~3.0mol/
L, oscillation mixing 100~200r/min of revolving speed, 30~60 DEG C of mixing temperature of oscillation, incorporation time 6~for 24 hours.It is centrifuged drying temperature
It is 100~200 DEG C, drying time is 2~12h.
Optimal parameter is metal salt solution concentration in 0.1~3.0mol/L, when dipping incorporation time is 12~18h, drying
Temperature is 140~180 DEG C, and drying time is 4~8h.At this moment the effect of silkworm excrement base charcoal material surface adsorbing metal salt is best.
High-ratio surface basic anhydride surface modification silkworm excrement base micropore carbon material of the invention can be applicable to medicine sustained and controlled release
In terms of aspect, especially pesticide delay 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.Using impregnation method in silkworm excrement base
Charcoal material surface adsorbing metal salt, then formed under the conditions of oxygen-enriched atmosphere in the material surface by way of plasma modification
Basic anhydride (metal oxide) modification.
In conventional pesticide molecule mostly containing polar group (carboxyl, carbonyl, sulfur-bearing and containing cl radical etc.), and this portion
Polarity group is also the dominant reactive part in pesticide, the suction that these polar groups can be formed with silkworm excrement neutral and alkali oxide
Attached position combines.Silkworm excrement base Carbon Materials can be adjusted by control silkworm excrement metal salt solution dipping and plasma modification condition
Basic sorbent site power and quantity, and then the adsorption capacity of pesticide and Carbon Materials can be regulated and controled, reach the slow-releasing and controlled-releasing action to 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 it is carried out under the voltage conditions of 20~30V
It is modified, it effectively increases basic anhydride and generates reaction speed.
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 after metal salt dipping, in O2Oxygen molecule under atmosphere
It is ionized as gas ions oxygen atom, and forms metal oxide with metal salt action, since selection metal oxide all has alkali
Property position, so forming the absorption of alkaline oxygenated position on the surface of the material.The using plasma modified-reaction time short (within 30min),
Plasma modification temperature is low (200 DEG C or less), with conventional high-temperature method for calcinating ratio (2~6h, 400~600 DEG C), has obvious
Advantage, and the method reduce high temperature O2Consumption to C, N atom in material had not only improved product yield but also had guaranteed material table
Face pattern and specific surface area.
4. by the quantity of the factor controllings such as plasma modification and metal salt immersion condition silkworm excrement surface alkalinty adsorption potential and
Type passes through plasma modification since basic sorbent site can have an important influence on the adsorption capacity between pesticide and material
Adsorption capacity between the controllable silkworm excrement base Carbon Materials of metal salt immersion condition and pesticide molecule, reaches the mesh for delaying controlled release to pesticide
's.
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 1 high-ratio surface basic anhydride surface modification silkworm excrement base micropore carbon material electron-microscope scanning figure of embodiment.
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 basic anhydride surface modification silkworm excrement base micropore carbon material, including walk as follows
Suddenly,
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 2.0h or more.
It (2) will carbonization silkworm excrement and KOH2With mass ratio 1:1 mixing, 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) by silkworm excrement base multi-stage porous Carbon Materials and 0.1mol/L Fe2(NO3)3Solution vibrates mixed according to plastid ratio 1:100
It is centrifuged and dries after conjunction, revolving speed 100r/min, 30 DEG C of temperature, incorporation time 6h, 100 DEG C of drying temperature, drying time 2h.
(4) material 1.0g after drying dipping is put into plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 20V, modification time 20min, it is modified cleared up 3 times with deionized water after low temperature drying obtain Gao Bibiao
Face basic anhydride modify 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 2.0h or more.
It (2) will carbonization silkworm excrement and KOH2With mass ratio 1:2 mixing, 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) by silkworm excrement base multi-stage porous Carbon Materials and 1.0mol/L Fe2(NO3)3Solution vibrates mixed according to plastid ratio 1:120
It is centrifuged and dries after conjunction, revolving speed 150r/min, 40 DEG C of temperature, time 8h, 120 DEG C of drying temperature, drying time 4h.
(4) material 1.0g after drying dipping is put into plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 22V, modification time 18min, it is modified cleared up 3 times with deionized water after low temperature drying obtain Gao Bibiao
Face basic anhydride modify 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 3.0h or more.
It (2) will carbonization silkworm excrement and KOH2With mass ratio 1:3 mixing, 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) by silkworm excrement base multi-stage porous Carbon Materials and 1.5mol/L Cu (NO3)2Solution according to plastid ratio 1:150 oscillation mixing,
It is centrifuged and dries after revolving speed 150r/min, 40 DEG C of temperature, time 12h, 150 DEG C of drying temperature, drying time 6h.
(4) material 1.0g after drying dipping is put into plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 24V, modification time 16min, it is modified cleared up 3 times with deionized water after low temperature drying obtain Gao Bibiao
Face basic anhydride modify 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 3.0h or more.
It (2) will carbonization silkworm excrement and KOH2With mass ratio 1:4 mixing, 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) by silkworm excrement base multi-stage porous Carbon Materials and 2.0mol/L Cu (NO3)2Solution according to plastid ratio 1:100 oscillation mixing,
It is centrifuged and dries after revolving speed 200r/min, temperature 50 C, time 16h, 200 DEG C of drying temperature, drying time 8h.
(4) material 1.0g after drying dipping is put into plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 26V, modification time 14min, it is modified cleared up 3 times with deionized water after low temperature drying obtain Gao Bibiao
Face basic anhydride modify 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 4.0h or more.
It (2) will carbonization silkworm excrement and KOH2With mass ratio 1:5 mixing, 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) by silkworm excrement base multi-stage porous Carbon Materials and 2.5mol/L AgNO3Solution mixes according to plastid ratio 1:100 oscillation, turns
It is centrifuged and dries after fast 200r/min, temperature 60 C, time 20h, 120 DEG C of drying temperature, drying time 8h.
(4) material 1.0g after drying dipping is put into plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 28V, modification time 12min, it is modified cleared up 3 times with deionized water after low temperature drying obtain Gao Bibiao
Face basic anhydride modify 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 4.0h 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) by silkworm excrement base multi-stage porous Carbon Materials and 3.0mol/L AgNO3Solution mixes according to plastid ratio 1:100 oscillation, turns
The centrifugation drying afterwards for 24 hours of fast 200r/min, temperature 60 C, time, 180 DEG C of drying temperature, drying time 12h.
(4) material 1.0g after drying dipping is put into plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 30V, modification time 10min, it is modified cleared up 3 times with deionized water after low temperature drying obtain Gao Bibiao
Face basic anhydride modify silkworm excrement base micropore carbon material.
Material properties test:
(1) electron microscope of high-ratio surface silkworm excrement base micropore carbon material
Using Japanese Hitachi S-3400N type low power scanning electron microscope to silkworm after Faeces bombycis slice, swelling freeze-drying
High-ratio surface basic anhydride surface modification obtained by silkworm excrement inner surface and the embodiment of the present invention 1 after sand slice, swelling freeze-drying
Silkworm excrement base 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 high-ratio surface basic anhydride table
Silkworm excrement base micropore carbon material electron-microscope scanning figure is modified in face, it can be seen that the silkworm excrement base Carbon Materials after plasma modification can be with shape
At porous structure.
(2) pore structure study of high-ratio surface silkworm excrement base micropore carbon 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
Face basic anhydride modify silkworm excrement base micropore carbon material and (embodiment 5 are selected to soak using the alkaline oxygenated surface modification of high-temperature calcination
Stain condition) silkworm excrement base Carbon Materials pore structure be measured, 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 for the alkaline oxygenated position surface modification silkworm excrement base micropore carbon material that plasma modification obtains
The data such as surface area and hole appearance illustrate that plasma modification can be to silkworm excrement with to there is slightly decline (about 10% or so) before modified
Base Microporous Carbon surface pore structure has some effects.And the alkaline oxygenated position face finish material obtained using high-temperature calcination mode
Because high temperature action leads to silkworm excrement, base Microporous Carbon surface pore structure is seriously damaged, and the data such as specific surface area and hole appearance only have
Before modified 60% or so, seriously affect its absorption property.This explanation prepares institute in the embodiment of the present invention coverage area
Obtained silkworm excrement base micropore carbon material is a kind of micropore carbon material with high specific surface area.
(3) different silkworm excrement base Carbon Materials constituent contents and product yield analysis
Using Japanese Hitachi S-3400N type low power scanning electron microscope energy spectrum analysis, to unmodified silkworm excrement base charcoal
Silkworm excrement base obtained by material, the embodiment of the present invention 1~6 and high-temperature calcination modification (selecting 5 immersion condition of embodiment) is micro-
Sample carries out the analysis of Fe, Cu, Ag elemental composition after hole Carbon Materials and above-mentioned material ultrasonic cleaning and product yield compares such as 2 institute of table
Show.
The different silkworm excrement base Carbon Materials doped chemical content tables of table 2
From 2 data of table it is found that unmodified silkworm excrement base Carbon Materials do not contain Fe, Cu and Ag element, after plasma modification
The metallic element that Examples 1 to 6 is not waited containing 0.8~1.5% respectively, and metallic element is not reduced after ultrasonic cleaning,
Illustrate that the material after plasma modification is respectively connected to Fe, Cu and Ag element and is firmly combined, and passes through high-temperature calcination
Its product yield of material afterwards is significantly less than other materials, illustrates plasma modification in product yield better than high-temperature calcination
Method.
(4) silkworm excrement base micropore carbon material sustained release performance is analyzed
Pesticide Diacloden absorption carriage amount is carried out to silkworm excrement base micropore carbon material prepared by case study on implementation 1,3,5 and sustained release is bent
Line analysis, wherein the adsorption conditions of Carbon Materials are that 50mg slow-release material is put into oscillation absorption in 50mL 0.8g/L Diacloden solution,
30 DEG C of bath temperature, vibrate 200 revs/min of revolving speed；The sustained release condition of Carbon Materials is that slow-release material is put into 120mL after 50mg is adsorbed
In deionized water, water 100mL is changed daily, 30 DEG C of bath temperature, vibrates 200 revs/min of revolving speed, experimental result is respectively such as Fig. 5, figure
Shown in 6.From figure 5 it can be seen that 3 kinds of slow-release materials all reach 500~560mg/g in absorption 48 hours back loading amounts of Diacloden
Between, and there is no difference between three kinds of materials, illustrate that such material can be protected while with different slow release effects
Hold similar adsorption effect.From fig. 6, it can be seen that (total to discharge in 15 days, 30 days and 60 days or so completion release processes respectively
90% Diacloden is measured as endpoint calculation), it is able to satisfy the requirement of different times pesticide slow-release.
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 basic anhydride modification silkworm excrement base micropore carbon material, it is characterised in that: it is slow in pesticide
Utilization in terms of controlled release；The material is three dimensional pore structures, and Langmuir specific surface area is 1000 ~ 1300 m2/ g, total pore volume
In 0.4-0.6 cm3/ g, wherein micropore specific area and Kong Rong account for 80% or more of total specific surface area and Kong Rong；Its preparation side
Method includes the 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 be carbonized silkworm excrement and KOH mixing, and activation reaming reaction is carried out in protective gas, then cleans, be centrifuged and dry again
High-ratio surface silkworm excrement base micropore carbon material is obtained after dry；
(3) it is centrifuged and dries after mixing high-ratio surface silkworm excrement base micropore carbon material with metal salt solution oscillation, place into plasma
Reactor according is passed through O2It is modified to carry out surface, 20 ~ 30 V of input voltage of plasma device, 10 ~ 20 min of modification time；It is modified
After clean, drying high-ratio surface basic anhydride surface modification silkworm excrement base micropore carbon material can be obtained,
The solid-liquid ratio of silkworm excrement base micropore carbon material and metal salt solution is 1:100 ~ 150 in the step (3)；In metal salt solution
Cation is Fe3+、Cu2+、Ag+, metal salt solution concentration is in 0.1 ~ 3.0 mol/L, oscillation 100 ~ 200 r/min of mixing, oscillation
30 ~ 60 oC of mixing temperature, 6 ~ 24 h of incorporation time；Centrifugation drying temperature is 100 ~ 200 oC, and drying time is 2 ~ 12 h.
2. the application of high-ratio surface basic anhydride modification silkworm excrement base micropore carbon material according to claim 1, feature
Be: silkworm excrement is 1:100 ~ 200 with water mixing plastid ratio in the step (1), and mixing temperature is 30 ~ 50 o C, incorporation time
For 0.5 ~ 3 h.
3. the application of high-ratio surface basic anhydride modification silkworm excrement base micropore carbon material according to claim 1, feature
Be: freezing dry process is first 2 ~ 4h of precooling at -25 o o of C ~ -20 C in the step (1), be then cooled to -
24 ~ 72h is lyophilized in the 60 o o of C ~ -40 C.
4. the application of high-ratio surface basic anhydride modification silkworm excrement base micropore carbon material according to claim 1, feature
Be: 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 basic anhydride modification silkworm excrement base micropore carbon material according to claim 1, feature
Be: 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 basic anhydride modification silkworm excrement base micropore carbon material according to claim 1, feature
Be: activation reaming reaction temperature has to be lower than carburizing temperature.
7. the application of high-ratio surface basic anhydride modification silkworm excrement base micropore carbon material according to claim 1, feature
Be: activation reaming reaction temperature is 650 ~ 950 oC in the step (2), and the reaction time is 0.5 ~ 5 h.
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