CN106423071B - A kind of high-ratio surface silkworm excrement porous charcoal MOFs composite material and preparation method and application - Google Patents
A kind of high-ratio surface silkworm excrement porous charcoal MOFs composite material and preparation method and application Download PDFInfo
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- CN106423071B CN106423071B CN201610813664.9A CN201610813664A CN106423071B CN 106423071 B CN106423071 B CN 106423071B CN 201610813664 A CN201610813664 A CN 201610813664A CN 106423071 B CN106423071 B CN 106423071B
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
-
- 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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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
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
Abstract
The invention discloses a kind of high-ratio surface silkworm excrement porous charcoal MOFs composite material and preparation methods and application.First by silkworm excrement and ZnCl2It is freeze-dried after solution mixing swelling, silkworm excrement after freeze-drying is carried out to activation reaming reaction in protective gas again, then it cleans again, silkworm excrement base multi-stage porous Carbon Materials are obtained after centrifugation and drying, it is centrifuged after metal salt solution is stirred with the material again, drying, it is passed through oxygen under the conditions of plasma modification and forms high dispersion metal oxide in silkworm excrement base multi-stage porous charcoal material surface, again by microwave irradiation method using high dispersion metal oxide as precursor, MOFs is grown on silkworm excrement base charcoal material surface, it finally filters and dries to obtain high-ratio surface silkworm excrement porous charcoal MOFs composite material.The material can be applied to pesticide and delay controlled release aspect.The obtained carbon composite of present invention specific surface area with higher and carboxylic group, 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 high-ratio surface silkworm excrement porous charcoal MOFs composite 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, 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 silkworm excrement porous charcoal MOFs composite material and preparation method with answer
With.The present invention first carries out swelling expanding treatment to silkworm excrement, then passes through activation processing, metal salt solution dipping, drying, plasma
Surface is modified and microwave radiation, obtained Carbon Materials specific surface area with higher and basic sorbent site, can have to pesticide compared with
High adsorption capacity and preferable slow-releasing and controlled-releasing action.
The purpose of the present invention is achieved through the following technical solutions:
High-ratio surface silkworm excrement porous charcoal MOFs composite material of the invention is three dimensional pore structures, Langmuir specific surface
Product is 2500~3000m2/ g, total pore volume is about in 1.50-2.50cm3/g。
The preparation method of high-ratio surface silkworm excrement porous charcoal MOFs composite material of the invention, includes the following steps:
(1) by Faeces bombycis and ZnCl2It is freeze-dried after solution mixing swelling；Silkworm excrement is in N after being lyophilized2, the protectiveness such as Ar gas
Reaming reaction is activated in gas, is then cleaned using dilute hydrochloric acid and deionized water flushing again, is dried to obtain silkworm excrement base multi-stage porous raw material of wood-charcoal
Material.
(2) by silkworm excrement base multi-stage porous Carbon Materials and metal salt solution, (cation is Cr3+、Fe2+Or Cu2+) oscillation mixing after
Centrifugation drying, places into plasma reactor, controls 20~50V of input voltage, is passed through O2It is modified to carry out surface, it is modified clear
It washes, high dispersive high specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material can be obtained in drying；
(3) by high dispersive high specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material and polybasic carboxylic acid ligand according to
Mass volume ratio is that 1:50~100 are mixed, and is put into microwave radiation in quartz ampoule and reacts, then cleans, is centrifuged, after drying
To high-ratio surface silkworm excrement porous charcoal MOFs composite material
As the further preferred of scheme, the ZnCl of step (1) Faeces bombycis and 0.25~0.30g/mL of mass concentration2Solution
Mixing plastid ratio is 1:100~200, and mixing temperature is 30~50 DEG C, and incorporation time is 0.5~3h.Freezing dry process is first
2~4h of precooling at -25 ° DEG C~-20C is then cooled to -60 DEG C~-40 DEG C 24~72h of freeze-drying.
As the further preferred of technical solution, ZnCl in the step (1)2Temperature is reacted with silkworm excrement activation reaming after freeze-drying
Degree is 300~700 DEG C, and the reaction time is 0.5~5h.
As the further preferred of technical solution, silkworm excrement base multi-stage porous Carbon Materials and metal salt feed liquid in the step (2)
Than for 1:50~100；1~30min of modification time.
As the further preferred of technical solution, the cation of metal salt solution is Cr3+、Fe2+Or Cu2+, metal salt solution
Concentration vibrates 30~60 DEG C of mixing temperature in 0.1~3.0mol/L, and incorporation time 6~for 24 hours；It is mixed with metal salt solution
Drying temperature is 100~200 DEG C, and drying time is 2~12h.
As the further preferred of technical solution, it is with the mixed drying temperature of metal salt solution in the step (2)
100~200 DEG C, drying time is 2~12h.
As the further preferred of technical solution, 1500~2000W of microwave power in the step (3), reaction temperature is
160~220 DEG C, 5~20min of reaction time, polybasic carboxylic acid ligand is terephthalic acids or trimesic acid.
In terms of high-ratio surface silkworm excrement porous charcoal MOFs composite material of the invention can be applicable to medicine sustained and controlled release, especially agriculture
In terms of medicine 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.It is added in swelling process simultaneously
ZnCl2Solution can make activator ZnCl2It is sufficiently mixed with silkworm excrement, more conducively next step obtains better activated material.
This patent application impregnation method silkworm excrement base charcoal material surface formed high dispersive metal salt absorption, then by etc. from
The modified mode of daughter forms high dispersion metal modified oxide in the material surface under the conditions of oxygen-enriched atmosphere.Again with metal oxygen
Compound MOFs Material growth precursor prepares high-ratio surface silkworm excrement porous charcoal MOFs composite material.Due to the polybasic carboxylic acid in raw material
Containing a large amount of carboxylic acid groups, carboxylic acid group can be formed in the composite material surface.Contain polarized mostly in conventional pesticide molecule
Group (carboxyl, carbonyl, sulfur-bearing and containing cl radical etc.), and this segment polarity group is also the dominant reactive part in pesticide,
These polar groups can be in conjunction with carboxylic acid group in silkworm excrement.Pass through control silkworm excrement metal salt solution dipping and MOFs microwave reaction
Growth conditions can regulate and control the quantity of carboxylic acid in the dispersion and MOFs material of MOFs material, and then can regulate and control pesticide and charcoal
The adsorption capacity of material reaches 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 group
And cellulose components, ZnCl2Activating mechanism be dissolution cellulose removing hydrone, use ZnCl2Expanding treatment silkworm excrement is activated,
High-ratio surface microcellular structure can be formed on activation silkworm excrement surface, by microcellular structure obtain to the higher absorption of pesticide appearance
Amount.
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. by ZnCl in swelling process2Solution is adsorbed onto silkworm excrement, by being freeze-dried ZnCl2It is fixed in silkworm excrement
Portion and surface, the method increase activator ZnCl2With the dispersion degree of silkworm excrement, more conducively activate in next step.
4. the present invention is prepared by way of the metal salt absorption that silkworm excrement base charcoal material surface forms high dispersive infusion process
High dispersive silkworm excrement MOFs composite material can make the growth of MOFs material have higher point compared with conventional MOFs prepares material
Property is dissipated, conducive to the specific surface area and carboxyl quantity for improving composite material.
5. the present invention is modified silkworm excrement base Carbon Materials after metal salt dipping by plasma mode, under oxygen atmosphere
Oxygen molecule is ionized as gas ions oxygen atom, and forms metal oxide with metal salt action.It is micro- using dipping-plasma-
The MOFs material of wave radiation method preparation grows more evenly more, specific surface compared with microwave irradiation on silkworm excrement base carbon material
Product is higher.
6. the present invention passes through the factor controllings silkworm excrement tables such as silkworm excrement metal salt solution dipping and MOFs microwave reaction growth conditions
The quantity of face carboxyl carboxylic acid group, since carboxylic acid group can have an important influence on the adsorption capacity between pesticide and material,
It is impregnated between the controllable silkworm excrement base Carbon Materials of MOFs microwave reaction growth conditions and pesticide molecule by silkworm excrement metal salt solution
Adsorption capacity, achieve the purpose that delay controlled release to pesticide.
7. 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 silkworm excrement porous charcoal MOFs composite material electron-microscope scanning figure of embodiment.
Fig. 5 is silkworm excrement base Carbon Materials XRD diagram.
Fig. 6 is that 5 high-ratio surface silkworm excrement porous charcoal MOFs composite material of embodiment and microwave irradiation XED scheme.
Fig. 7 difference slow-release material load capacity curve.
Fig. 8 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 silkworm excrement porous charcoal MOFs composite material, includes the following steps,
(1) by the ZnCl of Faeces bombycis and mass concentration 0.25g/mL2Solution is 1:100 progress according to plastid ratio at 30 DEG C
Silkworm excrement is pulled out after mixing swelling 3.0h, freeze-drying process is carried out to silkworm excrement, first the freezing pretreatment 4h at -20 DEG C, then is cooled down
For 24 hours to -60 DEG C of freeze-dryings, silkworm excrement after being lyophilized.
(2) silkworm excrement is in N after being lyophilized2300 DEG C are raised to the heating rate of 5 DEG C/min in atmosphere, and is protected at 300 DEG C
It holds 5.0h and carries out reaming reaction, to be cooled to room temperature naturally, obtained solid is dissolved in cleaning dissolution ZnCl in the HCl of 1mol/L2,
It reuses after deionized water is cleaned to pH ≈ 7 and is centrifuged, be placed in baking oven and be dried overnight, silkworm excrement base multi-stage porous raw material of wood-charcoal is obtained after drying
Material.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 0.1mol/L Fe2(NO3)3Solution according to plastid ratio 1:50 oscillation mixing,
It is centrifuged and dries after 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 30min, it is modified cleared up 3 times with deionized water after low temperature drying obtain high dispersive
High specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material.
(5) by high dispersive high specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material and terephthalic acids according to plastid
It mixes, is reacted in quartz ampoule, microwave power 1500W than 1:50, reaction temperature is 160 DEG C, then reaction time 5min is spent
Low temperature drying obtains high-ratio surface silkworm excrement porous charcoal MOFs composite material after ionized water is cleared up 3 times.
Embodiment 2
(1) by the ZnCl of Faeces bombycis and mass concentration 0.25g/mL2Solution is 1:120 progress according to plastid ratio at 35 DEG C
Silkworm excrement is pulled out after mixing swelling 2.5h, freeze-drying process is carried out to silkworm excrement, first the freezing pretreatment 3h at -20 DEG C, then is cooled down
To -55 DEG C of freeze-drying 36h, silkworm excrement after being lyophilized.
(2) silkworm excrement after freeze-drying is raised to 350 DEG C in an ar atmosphere with the heating rate of 5 DEG C/min, and is protected at 350 DEG C
It holds 4.0h and carries out reaming reaction, to be cooled to room temperature naturally, obtained solid is dissolved in cleaning dissolution ZnCl in the HCl of 1mol/L2,
It reuses after deionized water is cleaned to pH ≈ 7 and is centrifuged, be placed in baking oven and be dried overnight, silkworm excrement base multi-stage porous raw material of wood-charcoal is obtained after drying
Material.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 1.0mol/L Fe2(NO3)3Solution according to plastid ratio 1:80 oscillation mixing,
It is centrifuged and dries after revolving speed 120r/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 30V, modification time 5min, it is modified cleared up 3 times with deionized water after low temperature drying obtain high dispersive
High specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material.
(5) by high dispersive high specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material and terephthalic acids according to plastid
It mixes, is reacted in quartz ampoule, microwave power 1600W than 1:60, reaction temperature is 170 DEG C, then reaction time 8min is spent
Low temperature drying obtains high-ratio surface silkworm excrement porous charcoal MOFs composite material after ionized water is cleared up 3 times.
Embodiment 3
(1) by the ZnCl of Faeces bombycis and mass concentration 0.30g/mL2Solution is 1:140 progress according to plastid ratio at 40 DEG C
Silkworm excrement is pulled out after mixing swelling 2.0h, freeze-drying process is carried out to silkworm excrement, first the freezing pretreatment 2h at -25 DEG C, then is cooled down
To -50 DEG C of freeze-drying 48h, silkworm excrement after being lyophilized.
(2) silkworm excrement is in N after being lyophilized2400 DEG C are raised to the heating rate of 5 DEG C/min in atmosphere, and is protected at 400 DEG C
It holds 3.0h and carries out reaming reaction, to be cooled to room temperature naturally, obtained solid is dissolved in cleaning dissolution ZnCl in the HCl of 1mol/L2,
It reuses after deionized water is cleaned to pH ≈ 7 and is centrifuged, be placed in baking oven and be dried overnight, silkworm excrement base multi-stage porous raw material of wood-charcoal is obtained after drying
Material.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 1.5mol/L Cu (NO3)2Solution according to plastid ratio 1:100 oscillation mixing,
It is centrifuged and dries after revolving speed 140r/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 35V, modification time 20min, it is modified cleared up 3 times with deionized water after low temperature drying obtain high dispersive
High specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material.
(5) by high dispersive high specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material and terephthalic acids according to plastid
It mixes, is reacted in quartz ampoule, microwave power 1700W than 1:70, reaction temperature is 185 DEG C, then reaction time 11min is used
Low temperature drying obtains high-ratio surface silkworm excrement porous charcoal MOFs composite material after deionized water is cleared up 3 times.
Embodiment 4
(1) by the ZnCl of Faeces bombycis and mass concentration 0.25g/mL2Solution is 1:160 progress according to plastid ratio at 40 DEG C
Silkworm excrement is pulled out after mixing swelling 1.5h, freeze-drying process is carried out to silkworm excrement, first the freezing pretreatment 2.5h at -25 DEG C, then is dropped
Temperature is to -40 DEG C of freeze-drying 72h, silkworm excrement after being lyophilized.
(2) silkworm excrement is in N after being lyophilized2450 DEG C are raised to the heating rate of 5 DEG C/min in atmosphere, and is protected at 450 DEG C
It holds 2.0h and carries out reaming reaction, to be cooled to room temperature naturally, obtained solid is dissolved in cleaning dissolution ZnCl in the HCl of 1mol/L2,
It reuses after deionized water is cleaned to pH ≈ 7 and is centrifuged, be placed in baking oven and be dried overnight, silkworm excrement base multi-stage porous raw material of wood-charcoal is obtained after drying
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 160r/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 40V, modification time 15min, it is modified cleared up 3 times with deionized water after low temperature drying obtain high dispersive
High specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material.
(5) by high dispersive high specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material and trimesic acid according to plastid
It mixes, is reacted in quartz ampoule, microwave power 1800W than 1:80, reaction temperature is 200 DEG C, then reaction time 14min is used
Low temperature drying obtains high-ratio surface silkworm excrement porous charcoal MOFs composite material after deionized water is cleared up 3 times.
Embodiment 5
(1) by the ZnCl of Faeces bombycis and mass concentration 0.30g/mL2Solution is 1:180 progress according to plastid ratio at 45 DEG C
Silkworm excrement is pulled out after mixing swelling 1.0h, freeze-drying process is carried out to silkworm excrement, first the freezing pretreatment 4h at -20 DEG C, then is cooled down
To -45 DEG C of freeze-drying 60h, silkworm excrement after being lyophilized.
(2) silkworm excrement is in N after being lyophilized2550 DEG C are raised to the heating rate of 5 DEG C/min in atmosphere, and is protected at 550 DEG C
It holds 1.0h and carries out reaming reaction, to be cooled to room temperature naturally, obtained solid is dissolved in cleaning dissolution ZnCl in the HCl of 1mol/L2,
It reuses after deionized water is cleaned to pH ≈ 7 and is centrifuged, be placed in baking oven and be dried overnight, silkworm excrement base multi-stage porous raw material of wood-charcoal is obtained after drying
Material.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 2.5mol/L Cr (NO3)3Solution according to plastid ratio 1:100 oscillation mixing,
It is centrifuged and dries after revolving speed 180r/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 35V, modification time 15min, it is modified cleared up 3 times with deionized water after low temperature drying obtain high dispersive
High specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material.
(5) by high dispersive high specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material and trimesic acid according to plastid
It mixes, is reacted in quartz ampoule, microwave power 1900W than 1:90, reaction temperature is 210 DEG C, then reaction time 17min is used
Low temperature drying obtains high-ratio surface silkworm excrement porous charcoal MOFs composite material after deionized water is cleared up 3 times.
Embodiment 6
(1) by the ZnCl of Faeces bombycis and mass concentration 0.25g/mL2Solution is 1:200 progress according to plastid ratio at 50 DEG C
Silkworm excrement is pulled out after mixing swelling 0.5h, freeze-drying process is carried out to silkworm excrement, first the freezing pretreatment 4h at -20 DEG C, then is cooled down
To -40 DEG C of freeze-drying 72h, silkworm excrement after being lyophilized.
(2) silkworm excrement is in N after being lyophilized2700 DEG C are raised to the heating rate of 5 DEG C/min in atmosphere, and is protected at 700 DEG C
It holds 0.5h and carries out reaming reaction, to be cooled to room temperature naturally, obtained solid is dissolved in cleaning dissolution ZnCl in the HCl of 1mol/L2,
It reuses after deionized water is cleaned to pH ≈ 7 and is centrifuged, be placed in baking oven and be dried overnight, silkworm excrement base multi-stage porous raw material of wood-charcoal is obtained after drying
Material.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 3.0mol/L Cr (NO3)3Solution according to plastid ratio 1:100 oscillation mixing,
The centrifugation drying afterwards for 24 hours of revolving speed 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 50V, modification time 1~2min, it is modified cleared up 3 times with deionized water after low temperature drying obtain high score
Dissipate high specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material.
(5) by high dispersive high specific surface area metal oxide silkworm excrement porous charcoal MOFs composite material and trimesic acid according to plastid
It mixes, is reacted in quartz ampoule, microwave power 2000W than 1:100, reaction temperature is 220 DEG C, then reaction time 20min is used
Low temperature drying obtains high-ratio surface silkworm excrement porous charcoal MOFs composite material after deionized water is cleared up 3 times.
Material property detection:
(1) electron microscope of material
Using Japanese Hitachi S-3400N type low power scanning electron microscope to silkworm after Faeces bombycis slice, swelling freeze-drying
High-ratio surface silkworm excrement porous charcoal MOFs obtained by silkworm excrement inner surface and the embodiment of the present invention 1 is compound after sand slice, swelling freeze-drying
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 silkworm excrement porous charcoal
MOFs composite material electron-microscope scanning figure, it can be seen that composite material can form porous structure.
(2) specific surface area analysis
Use Micro company, the U.S. produce 3-Flex specific surface pore-size distribution instrument with non-swelling treatment silkworm excrement and swelling at
Silkworm excrement is that raw material prepares silkworm excrement porous carbon material (according to 1 activation condition of embodiment), to silkworm excrement base prepared by the present invention after reason
Microwave irradiation high-ratio surface silkworm excrement porous charcoal MOFs is multiple under multi-stage porous Carbon Materials, the embodiment of the present invention 1,3,5 and the same terms
The specific surface area numerical value of condensation material is compared, and the results are shown in Table 1.
1 different materials specific surface area analysis of table
According to 1 column data of table it is found that silkworm excrement base multi-stage porous Carbon Materials Langmuir specific surface area prepared by embodiment
In 2500~3000m2/ g, porosity are in 0.75~0.85cm3/ g, and directly it is swollen the compound silkworm excrement base porous charcoal of no MOFs
The specific surface area and porosity of Carbon Materials only have it is compound after 45% or so, be not swollen and the silkworm excrement Quito hole compound without MOFs
The specific surface area and porosity of charcoal Carbon Materials only has compound rear 25% or so, this explanation can be substantially by the compound of MOFS material
The specific surface area and porosity of material is improved, while being swollen compared with non-swollen material, is not swollen the ratio table of silkworm excrement base Carbon Materials
Area and porosity are only 60% or so of silkworm excrement base Carbon Materials after being swollen, and silkworm excrement can improve silkworm excrement Quito hole after this illustrates swelling
The specific surface area and porosity of Carbon Materials.Simultaneously by composite material prepared by embodiment and using the compound of microwave irradiation preparation
Material compares discovery, and the specific surface area of microwave irradiation material is about 80~90% left sides of the same terms embodiment material
The right side illustrates the yield that MOFs on silkworm excrement base multi-stage porous charcoal can be improved using dipping-plasma-microwave irradiation.
(3) different silkworm excrement base Carbon Materials XRD analysis
Using the X-ray diffractometer of Japanese Rigaku D/MAX to silkworm excrement base multi-stage porous charcoal prepared by the present invention, implementation
Composite material prepared by example 5 and 5 microwave radiation material of embodiment carry out XRD test, test condition are as follows: Cu K α target, scanning speed
0.2 °/min, 30kV, test result is as shown in Figure 5,6.From the comparison of Fig. 5 and Fig. 6 it is found that compound rear silkworm excrement porous charcoal MOFs material
Material has typical MOFs crystal structure figure, and composite material prepared by embodiment 5 and 5 microwave radiation material of embodiment in Fig. 6
Expect and disperse wider compared to peak, illustrates that composite material prepared by embodiment 5 has lower crystallinity, and simultaneously as known from Table 1
Composite material prepared by example 5 has better specific surface area than 5 microwave radiation material of embodiment, to illustrate multiple prepared by example 5
Condensation material has preferably crystallization dispersion degree than 5 microwave radiation material of embodiment.
(4) material sustained release performance analysis
The absorption of pesticide Diacloden is carried out to high-ratio surface silkworm excrement porous charcoal MOFs composite material prepared by case study on implementation 1,3,5
Load capacity and sustained release tracing analysis, wherein the adsorption conditions of Carbon Materials are that 25mg slow-release material is put into 50mL 0.8g/L Diacloden
Absorption is vibrated in solution, 30 DEG C of bath temperature, vibrates 200 revs/min of revolving speed；The sustained release condition of Carbon Materials is to delay after 25mg is adsorbed
It releases material to be put into 120mL deionized water, changes water 100mL daily, 30 DEG C of bath temperature, vibrate 200 revs/min of revolving speed, experiment
As a result as shown in Figure 7, Figure 8 respectively.It can be seen from figure 7 that 3 kinds of slow-release materials are adsorbing 48 hours back loading amounts of Diacloden all
Reach between 500~560mg/g, and there is no difference between three kinds of materials, illustrates that such material has different delay
Similar adsorption effect is able to maintain while releasing effect.From figure 8, it is seen that being completed respectively at 15 days, 30 days and 60 days or so
Release process (using 90% Diacloden of total volume as endpoint calculation), 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 (9)
1. a kind of preparation method of high-ratio surface silkworm excrement porous charcoal MOFs composite material, it is characterised in that: include the following steps,
(1) by Faeces bombycis and ZnCl2It is freeze-dried after solution mixing swelling, then silkworm excrement after freeze-drying is lived in protective gas
Change reaming reaction, silkworm excrement base porous carbon material is obtained after then cleaning, be centrifuged and drying again；
(2) it is centrifuged and dries after mixing silkworm excrement base porous carbon material with metal salt solution oscillation, place into plasma reactor,
20 ~ 50 V of input voltage is controlled, O is passed through2It is modified to carry out surface, high dispersive high-ratio surface can be obtained in modified cleaning, drying
Metal oxide silkworm excrement porous carbon composite material；
(3) by high dispersive high specific surface area metal oxide silkworm excrement porous carbon composite material and polybasic carboxylic acid ligand according to quality volume
Than being mixed for 1:50 ~ 100, it is put into microwave radiation in quartz ampoule and reacts, then clean, be centrifuged, obtain Gao Bibiao after drying
Face silkworm excrement porous charcoal MOFs composite material；The high-ratio surface silkworm excrement porous charcoal MOFs composite material is three dimensional pore structures,
Langmuir specific surface area is 2500 ~ 3000 m2/g。
2. the preparation method of high-ratio surface silkworm excrement porous charcoal MOFs composite material according to claim 1, it is characterised in that:
The ZnCl of Faeces bombycis and 0.25 ~ 0.30 g/mL of mass concentration in the step (1)2Solution mixing plastid ratio be 1:100 ~
200, mixing temperature is 30 ~ 50 DEG C, and incorporation time is 0.5 ~ 3 h.
3. the preparation method of high-ratio surface silkworm excrement porous charcoal MOFs composite material according to claim 1, it is characterised in that:
In the step (1) freezing dry process be first at -25 DEG C ~ -20 DEG C 2 ~ 4h of precooling, be then cooled to -60 DEG C ~
- 40 DEG C of 24 ~ 72h of freeze-drying.
4. the preparation method of high-ratio surface silkworm excrement porous charcoal MOFs composite material according to claim 1, it is characterised in that:
Silkworm excrement base porous carbon material and metal salt solution solid-liquid ratio are 1:50 ~ 100 in the step (2)；The cation of metal salt solution
For Cr3+、Fe2+Or Cu2+, metal salt solution concentration vibrates 30 ~ 60 DEG C of mixing temperature in 0.1 ~ 3.0 mol/L, and incorporation time 6 ~
24 h；It is 100 ~ 200 DEG C with the mixed drying temperature of metal salt solution, drying time is 2 ~ 12 h.
5. the preparation method of high-ratio surface silkworm excrement porous charcoal MOFs composite material according to claim 1, it is characterised in that:
1 ~ 30 min of modification time in the step (2).
6. the preparation method of high-ratio surface silkworm excrement porous charcoal MOFs composite material according to claim 1, it is characterised in that:
1500 ~ 2000 W of microwave power in the step (3), reaction temperature are 160 ~ 220 DEG C, 5 ~ 20 min of reaction time.
7. the preparation method of high-ratio surface silkworm excrement porous charcoal MOFs composite material according to claim 1, it is characterised in that:
Polybasic carboxylic acid ligand is terephthalic acids or trimesic acid.
8. the preparation method of high-ratio surface silkworm excrement porous charcoal MOFs composite material according to claim 1, it is characterised in that:
Silkworm excrement activation reaming reaction temperature is 300 ~ 700 DEG C after freeze-drying in the step (1), and the reaction time is 0.5 ~ 5 h.
9. the application for the high-ratio surface silkworm excrement porous charcoal MOFs composite material that preparation method as described in claim 1 obtains,
It is characterized in that: its application in terms of pesticide delays controlled release.
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| CN103221126A (en) * | 2011-03-31 | 2013-07-24 | 科学与工业研究委员会 | Activated carbon-metal organic framework composite materials with enhanced gas adsorption capacity and process for the preparation thereof |
| CN103566874A (en) * | 2013-09-26 | 2014-02-12 | 蚌埠华纺滤材有限公司 | Silkworm excrement modified porous active carbon and preparation method thereof |
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| CN103221126A (en) * | 2011-03-31 | 2013-07-24 | 科学与工业研究委员会 | Activated carbon-metal organic framework composite materials with enhanced gas adsorption capacity and process for the preparation thereof |
| CN103566874A (en) * | 2013-09-26 | 2014-02-12 | 蚌埠华纺滤材有限公司 | Silkworm excrement modified porous active carbon and preparation method thereof |
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