CN106378100B - A kind of infusion process silkworm excrement porous charcoal MOFs composite material and preparation methods and application - Google Patents
A kind of infusion process silkworm excrement porous charcoal MOFs composite material and preparation methods and application Download PDFInfo
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- CN106378100B CN106378100B CN201610812073.XA CN201610812073A CN106378100B CN 106378100 B CN106378100 B CN 106378100B CN 201610812073 A CN201610812073 A CN 201610812073A CN 106378100 B CN106378100 B CN 106378100B
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Abstract
The invention discloses a kind of infusion process silkworm excrement porous charcoal MOFs composite material and preparation methods and application.It is freeze-dried after silkworm excrement first to be mixed to swelling with water, silkworm excrement after freeze-drying is carried out to carbonization 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 hydrothermal synthesis 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 infusion process silkworm excrement porous charcoal MOFs composite materials.The obtained carbon composite of the present invention has higher specific surface area 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 infusion process silkworm excrement porous charcoal MOFs composite materials and its preparation
Method and application.
Background technology
Pesticide can efficiently control the harm of disease, worm, grass and other harmful organisms to crops, it is as chemical prevention
Important means, irreplaceable role is played 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 ratio low.This part is not
Playing the pesticide of 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.How to effectively improve the utilization ratio of pesticide and Targeting delivery function is urgently to be resolved hurrily main of current pesticide field
One of problem.
Slow controlled-release technology, which is one kind, so that pesticide activity component is slowly released 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, and silkworm excrement base charcoal derives from the main waste silkworm excrement in silkworm industry,
Often arbitrarily being abandoned 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 through high temperature cabonization, and abundant N (O) group is also contained on its surface, leads to
Its slow controlled release ability can be promoted to its modification by crossing.
Invention content
The object of the present invention is to provide a kind of infusion process silkworm excrement porous charcoal MOFs composite material and preparation methods and application.
The present invention first carries out swelling expanding treatment to silkworm excrement, then carries out carbonization treatment to silkworm excrement after freeze-drying, then is soaked by metal salt solution
Stain, drying and plasma surface modification, obtained Carbon Materials have higher specific surface area and basic sorbent site, can be to agriculture
Medicine has higher adsorption capacity and preferable slow-releasing and controlled-releasing action.
The purpose of the present invention is achieved through the following technical solutions：
The preparation method of the infusion process silkworm excrement porous charcoal MOFs composite materials of the present invention, 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
Be carbonized reaming reaction, then cleans again after being rinsed 3 times using dilute hydrochloric acid and deionized water and dries to obtain silkworm excrement base multi-stage porous Carbon Materials；
(2) it centrifuges and dries after mixing silkworm excrement base multi-stage porous Carbon Materials with metal salt solution oscillation, place into plasma
Reactor, 20~30V of input voltage of plasma device, 10~20min of modification time are passed through O2Surface modification is carried out, it is modified
After clean, drying can be obtained high dispersion metal oxide silkworm excrement porous charcoal MOFs composite materials；
(3) by high dispersion metal oxide silkworm excrement porous charcoal MOFs composite materials and polybasic carboxylic acid ligand according to quality volume
Than being 1:50~100 are mixed, and are put into autoclave and are reacted, are impregnated after then cleaning, centrifuge and drying again
Method silkworm excrement porous charcoal MOFs composite materials.
As the further preferred of scheme, step (1) Faeces bombycis is 1 with water mixing plastid ratio:100~200, mixing temperature
It 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 technical solution, activation reaming reaction temperature is 300~700 DEG C in step (1), when reaction
Between be 0.5~5h.
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, incorporation time 6 in 0.1~3.0mol/L, oscillation mixing 100~200r/min of rotating speed
~for 24 hours.
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, reaction temperature is 160~220 DEG C in the step (3), the reaction time 12
~22h；Polybasic carboxylic acid ligand is terephthalic acids or trimesic acid.
The infusion process silkworm excrement porous charcoal MOFs composite materials of the present invention are three dimensional pore structures, Langmuir specific surface areas
For 2300~2800m2/ g, total pore volume is about in 1.50-2.50cm3/g。
The infusion process silkworm excrement porous charcoal MOFs composite materials of the present invention can be applicable to medicine sustained and controlled release aspect, especially pesticide
In terms of slow controlled release.
Products application of the present invention delays controlled release field in pesticide, and anabasine pesticide Diacloden, absorption are adsorbed 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：Make since limited swelling can occur in aqueous solution for special macromolecular structure 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 formed high dispersive metal salt absorption, then by way of plasma modification under the conditions of oxygen-enriched atmosphere at this
Material surface forms high dispersion metal modified oxide.Again with metal oxide MOFs Material growth precursors, it is porous to prepare silkworm excrement
Charcoal MOFs composite materials.Since the polybasic carboxylic acid in raw material contains a large amount of carboxylic acid groups, carboxylic can be formed in the composite material surface
Acid groups.Contain mostly in conventional pesticide molecule polar group (carboxyl, carbonyl, sulfur-bearing and containing cl radical etc.), and this portion
Polarity group is also the dominant reactive part in pesticide, these polar groups can be combined with carboxylic acid group in silkworm excrement.Pass through
Control silkworm excrement metal salt solution dipping and MOFs hydration reactions growth conditions can regulate and control the deployment conditions and MOFs of MOFs materials
The quantity of carboxylic acid in material, 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 refers to just 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, a large amount of oxygen atom in the carbonization treatment under protecting gas can seize material, on carbonization silkworm excrement surface
High-ratio surface microcellular structure is formed, the relatively high-adsorption-capacity to pesticide is obtained by microcellular structure；And in the voltage item of 20~30V
It is modified under part, effectively increases metal oxide reaction of formation 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. the present invention is prepared infusion process by way of the metal salt absorption that silkworm excrement base charcoal material surface forms high dispersive
High dispersive silkworm excrement MOFs composite materials can make the growth of MOFs materials have higher point compared with conventional MOFs prepares material
Property is dissipated, is conducive to improve the specific surface area and carboxyl quantity of composite material.
4. silkworm excrement base multi-stage porous Carbon Materials are modified after the present invention impregnates metal salt by plasma mode, in oxygen
Oxygen molecule is ionized as gas ions oxygen atom under atmosphere, and forms metal oxide with metal salt action.Using dipping-plasma
MOFs materials prepared by body-hydration method are grown evenly, specific surface area is more compared with conventional aqueous method on silkworm excrement base carbon material
It is high.
5. the present invention passes through the factor controllings silkworm excrement tables such as silkworm excrement metal salt solution dipping and MOFs hydration 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,
Pass through silkworm excrement metal salt solution dipping and the controllable silkworm excrement base multi-stage porous Carbon Materials of MOFs hydration reaction growth conditions and pesticide point
Adsorption capacity between son achievees the purpose that delay controlled release to pesticide.
6. the 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).
Description of the drawings
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 silkworm excrement porous charcoal MOFs composite material electron-microscope scanning figures of embodiment.
Fig. 5 is silkworm excrement base Carbon Materials XRD diagram.
Fig. 6 is 5 silkworm excrement porous charcoal MOFs composite materials of embodiment and hydration method XED figures.
Fig. 7 difference slow-release material load capacity curves.
Fig. 8 difference slow-release materials are sustained release profiles.
Specific implementation mode
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 infusion process silkworm excrement porous charcoal MOFs composite materials, includes the following steps,
(1) it is 1 according to plastid ratio by Faeces bombycis and deionized water:100 carry out mixing swelling, after being swollen 3.0h at 30 DEG C
Silkworm excrement is pulled out and is freeze-dried, first the freezing pretreatment 4h at -20 DEG C, then reduces temperature to -60 DEG C of freeze-dryings and is lyophilized for 24 hours
Silkworm excrement afterwards.
(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, wait for that nature is cooled to room temperature, obtained solid is dissolved in cleaning material in the HCl of 1mol/L, then make
It is centrifuged after being cleaned to pH ≈ 7 with deionized water, is placed in baking oven and is dried overnight, silkworm excrement base multi-stage porous Carbon Materials are obtained after drying.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 0.1mol/L Fe2(NO3)3Solution is according to plastid than 1:50 oscillation mixing,
Drying, 100 DEG C of drying temperature, drying time 2h are centrifuged after rotating speed 100r/min, 30 DEG C of temperature, incorporation time 6h.
(4) material 1.0g is put into plasma reactor after impregnating drying, 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 high dispersive
Metal oxide silkworm excrement porous charcoal MOFs composite materials.
(5) by high dispersion metal oxide silkworm excrement porous charcoal MOFs composite materials and terephthalic acids according to plastid ratio 1:50 is mixed
It closes, is reacted in autoclave, reaction temperature is 160 DEG C, reaction time 12h, low temperature after then being cleared up 3 times with deionized water
It is dried to obtain infusion process silkworm excrement porous charcoal MOFs composite materials.
Embodiment 2
(1) it is 1 according to plastid ratio by Faeces bombycis and deionized water:120 carry out mixing swelling, after being swollen 2.5h at 35 DEG C
Silkworm excrement is pulled out and is freeze-dried, first the freezing pretreatment 3h at -20 DEG C, then reduces temperature extremely -55 DEG C of freeze-drying 36h and is lyophilized
Silkworm excrement afterwards.
(2) 350 DEG C will be raised to the heating rate of 5 DEG C/min in silkworm excrement Ar atmosphere after freeze-drying, and be kept at 350 DEG C
4.0h carries out reaming reaction, waits for that nature is cooled to room temperature, obtained solid is dissolved in cleaning material in the HCl of 1mol/L, is reused
Deionized water centrifuges after cleaning to pH ≈ 7, is placed in baking oven and is dried overnight, and silkworm excrement base multi-stage porous Carbon Materials are obtained after drying.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 1.0mol/L Fe2(NO3)3Solution is according to plastid than 1:80 oscillation mixing,
Drying, 120 DEG C of drying temperature, drying time 4h are centrifuged after rotating speed 120r/min, 40 DEG C of temperature, time 8h.
(4) material 1.0g is put into plasma reactor after impregnating drying, 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 high dispersive
Metal oxide silkworm excrement porous charcoal MOFs composite materials.
(5) by high dispersion metal oxide silkworm excrement porous charcoal MOFs composite materials and terephthalic acids according to plastid ratio 1:60 is mixed
It closes, is reacted in autoclave, reaction temperature is 170 DEG C, reaction time 14h, low temperature after then being cleared up 3 times with deionized water
It is dried to obtain infusion process silkworm excrement porous charcoal MOFs composite materials.
Embodiment 3
(1) it is 1 according to plastid ratio by Faeces bombycis and deionized water:140 carry out mixing swelling, after being swollen 2.0h at 40 DEG C
Silkworm excrement is pulled out and is freeze-dried, first the freezing pretreatment 2h at -25 DEG C, then reduces temperature extremely -50 DEG C of freeze-drying 48h and is lyophilized
Silkworm excrement afterwards.
(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, wait for that nature is cooled to room temperature, obtained solid is dissolved in cleaning material in the HCl of 1mol/L, then make
It is centrifuged after being cleaned to pH ≈ 7 with deionized water, is placed in baking oven and is dried overnight, silkworm excrement base multi-stage porous Carbon Materials are obtained after drying.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 1.5mol/L Cu (NO3)2Solution is according to plastid than 1:100 oscillation mixing,
Drying, 150 DEG C of drying temperature, drying time 6h are centrifuged after rotating speed 140r/min, 40 DEG C of temperature, time 12h.
(4) material 1.0g is put into plasma reactor after impregnating drying, 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 high dispersive
Metal oxide silkworm excrement porous charcoal MOFs composite materials.
(5) by high dispersion metal oxide silkworm excrement porous charcoal MOFs composite materials and terephthalic acids according to plastid ratio 1:70 is mixed
It closes, is reacted in autoclave, reaction temperature is 185 DEG C, reaction time 16h, low temperature after then being cleared up 3 times with deionized water
It is dried to obtain infusion process silkworm excrement porous charcoal MOFs composite materials.
Embodiment 4
(1) it is 1 according to plastid ratio by Faeces bombycis and deionized water:160 carry out mixing swelling, after being swollen 1.5h at 40 DEG C
Silkworm excrement is pulled out and is freeze-dried, first the freezing pretreatment 2.5h at -25 DEG C, then reduces temperature extremely -40 DEG C of freeze-drying 72h and is frozen
Silkworm excrement after dry.
(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, wait for that nature is cooled to room temperature, obtained solid is dissolved in cleaning material in the HCl of 1mol/L, then make
It is centrifuged after being cleaned to pH ≈ 7 with deionized water, is placed in baking oven and is dried overnight, silkworm excrement base multi-stage porous Carbon Materials are obtained after drying.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 2.0mol/L Cu (NO3)2Solution is according to plastid than 1:100 oscillation mixing,
Drying, 200 DEG C of drying temperature, drying time 8h are centrifuged after rotating speed 160r/min, temperature 50 C, time 16h.
(4) material 1.0g is put into plasma reactor after impregnating drying, 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 high dispersive
Metal oxide silkworm excrement porous charcoal MOFs composite materials.
(5) by high dispersion metal oxide silkworm excrement porous charcoal MOFs composite materials and trimesic acid according to plastid ratio 1:80 is mixed
It closes, is reacted in autoclave, reaction temperature is 200 DEG C, reaction time 18h, low temperature after then being cleared up 3 times with deionized water
It is dried to obtain infusion process silkworm excrement porous charcoal MOFs composite materials.
Embodiment 5
(1) it is 1 according to plastid ratio by Faeces bombycis and deionized water:180 carry out mixing swelling, after being swollen 1.0h at 45 DEG C
Silkworm excrement is pulled out and is freeze-dried, first the freezing pretreatment 4h at -20 DEG C, then reduces temperature extremely -45 DEG C of freeze-drying 60h and is lyophilized
Silkworm excrement afterwards.
(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, wait for that nature is cooled to room temperature, obtained solid is dissolved in cleaning material in the HCl of 1mol/L, then make
It is centrifuged after being cleaned to pH ≈ 7 with deionized water, is placed in baking oven and is dried overnight, silkworm excrement base multi-stage porous Carbon Materials are obtained after drying.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 2.5mol/L Cr (NO3)3Solution is according to plastid than 1:100 oscillation mixing,
Drying, 120 DEG C of drying temperature, drying time 8h are centrifuged after rotating speed 180r/min, temperature 60 C, time 20h.
(4) material 1.0g is put into plasma reactor after impregnating drying, 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 high dispersive
Metal oxide silkworm excrement porous charcoal MOFs composite materials.
(5) by high dispersion metal oxide silkworm excrement porous charcoal MOFs composite materials and trimesic acid according to plastid ratio 1:90 is mixed
It closes, is reacted in autoclave, reaction temperature is 210 DEG C, reaction time 20h, low temperature after then being cleared up 3 times with deionized water
It is dried to obtain infusion process silkworm excrement porous charcoal MOFs composite materials.
Embodiment 6
(1) it is 1 according to plastid ratio by Faeces bombycis and deionized water:200 carry out mixing swelling, after being swollen 0.5h at 50 DEG C
Silkworm excrement is pulled out and is freeze-dried, first the freezing pretreatment 4h at -20 DEG C, then reduces temperature extremely -40 DEG C of freeze-drying 72h and is lyophilized
Silkworm excrement afterwards.
(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, wait for that nature is cooled to room temperature, obtained solid is dissolved in cleaning material in the HCl of 1mol/L, then make
It is centrifuged after being cleaned to pH ≈ 7 with deionized water, is placed in baking oven and is dried overnight, silkworm excrement base multi-stage porous Carbon Materials are obtained after drying.
(3) by silkworm excrement base multi-stage porous Carbon Materials and 3.0mol/L Cr (NO3)3Solution is according to plastid than 1:100 oscillation mixing,
The centrifugation drying afterwards for 24 hours of rotating speed 200r/min, temperature 60 C, time, 180 DEG C of drying temperature, drying time 12h.
(4) material 1.0g is put into plasma reactor after impregnating drying, 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 high dispersive
Metal oxide silkworm excrement porous charcoal MOFs composite materials.
(5) by high dispersion metal oxide silkworm excrement porous charcoal MOFs composite materials and trimesic acid according to plastid ratio 1:100
Mixing, reacts in autoclave, and reaction temperature is 220 DEG C, reaction time 22h, low after then being cleared up 3 times with deionized water
Temperature is dried to obtain infusion process silkworm excrement porous charcoal MOFs composite materials.
Material property detects：
(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
Silkworm excrement porous charcoal MOFs composite materials after sand slice, swelling freeze-drying obtained by silkworm excrement inner surface and the embodiment of the present invention 1 carry out
The characterization of material surface pattern, as shown in Figure 1, Figure 2, Figure 3, Figure 4.
By Fig. 1 and Fig. 2 comparisons 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 infusion process 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 of silkworm excrement base multi-stage porous Carbon Materials
Use Micro companies 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 1 carbonization condition of embodiment), the present invention after processing silkworm excrement and swelling treatment
The specific surface area numerical value of direct hydration method silkworm excrement porous charcoal MOFs composite materials is compared under embodiment 1,3,5 and the same terms
Compared with 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 infusion process silkworm excrement porous charcoal MOFs composite materials prepared by embodiment
Langmuir specific surface areas are in 2300~2800m2/ g, porosity are in 0.6~0.8cm3Between/g, and directly it is swollen no MOFs
The specific surface area and porosity of compound silkworm excrement base porous charcoal Carbon Materials only have it is compound after 50% or so, be not swollen and do not have
The specific surface area and porosity of silkworm excrement base porous charcoal Carbon Materials compound MOFs only has compound rear 30% or so, this illustrates process
The compound specific surface area and porosity that can greatly improve material of MOFS materials, while being swollen compared with non-swollen material, not
The specific surface area and porosity for being swollen silkworm excrement base Carbon Materials is only 60% or so of silkworm excrement base Carbon Materials after being swollen, this illustrates to be swollen
Silkworm excrement can improve the specific surface area and porosity of silkworm excrement base porous carbon material afterwards.While it by composite material prepared by embodiment and adopting
The composite material prepared with hydration method carries out comparison discovery, and the specific surface area of hydration method material is about the same terms embodiment material
70~80% or so, illustrate that MOFs on silkworm excrement base multi-stage porous Carbon Materials can be improved using dipping-plasma-hydration method
Yield.
(3) different silkworm excrement base Carbon Materials XRD analysis
Using the X-ray diffractometer of Japanese Rigaku D/MAX to the silkworm excrement base Carbon Materials prepared by the present invention, embodiment 5
Prepared composite material and 5 hydrated material of embodiment carry out XRD tests, and test condition is：CuK α targets, 0.2 ° of sweep speed/
Min, 30kV, test result are as shown in Figure 5,6.From the comparison of Fig. 5 and Fig. 6 it is found that silkworm excrement porous charcoal MOFs materials have after compound
There are typical MOFs crystal structures figure, and the peak compared with 5 hydrated material of embodiment of composite material prepared by embodiment 5 in Fig. 6
Wider and disperse illustrates that composite material prepared by embodiment 5 has lower crystallinity, and simultaneously as known from Table 1 prepared by example 5
Composite material has better specific surface area than 5 hydrated material of embodiment, to illustrate that composite material prepared by example 5 compares embodiment
5 hydrated materials have preferably crystallization dispersion degree.
(4) material slow-release performance evaluation
It is negative that the absorption of pesticide Diacloden is carried out to infusion process silkworm excrement porous charcoal MOFs composite materials prepared by case study on implementation 1,3,5
Carrying capacity and sustained release tracing analysis, the wherein adsorption conditions of Carbon Materials are that be put into 50mL 0.8g/L Diaclodens molten for 25mg slow-release materials
Absorption is vibrated in liquid, 30 DEG C of bath temperature vibrates 200 revs/min of rotating speed；The sustained release condition of Carbon Materials is to be sustained after 25mg is adsorbed
Material is put into 120mL deionized waters, changes water 100mL daily, and 30 DEG C of bath temperature vibrates 200 revs/min of rotating speed, experiment knot
Fruit difference is as shown in Figure 7, Figure 8.It can be seen from figure 7 that 3 kinds of slow-release materials are all reached in absorption 48 hours back loading amounts of Diacloden
To between 500~560mg/g, and there is no difference between three kinds of materials, illustrates such material with different sustained releases
Similar adsorption effect can be kept while effect.From figure 8, it is seen that being released respectively in completion in 15 days, 30 days and 60 days or so
Journey (using 90% Diacloden of total volume as endpoint calculation) is let off, the requirement of different times pesticide slow-release can be met.
The above embodiment of the present invention is only intended to clearly illustrate examples made by the present invention, and is not to the present 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.All spirit in the present invention
With within principle made by all any modification, equivalent and improvement etc., should be included in the protection domain of the claims in the present invention
Within.
Claims (9)
1. a kind of preparation method of silkworm excrement porous charcoal MOFs composite materials, it is characterised in that：Include the following steps,
（1）Faeces bombycis is freeze-dried after mixing swelling with water, then that silkworm excrement after freeze-drying is carried out in protective gas to carbonization reaming is anti-
It answers, silkworm excrement base porous carbon material is obtained after then cleaning, centrifuge and drying；
（2）It centrifuges and dries after silkworm excrement base porous carbon material is mixed with metal salt solution oscillation, place into plasma reactor,
20 ~ 30 V of input voltage of plasma device, 10 ~ 20 min of modification time；It is passed through O2Progress surface modification, modified cleaning,
Drying can be obtained high dispersion metal oxide silkworm excrement porous carbon composite material；
（3）According to mass volume ratio it is 1 by high dispersion metal oxide silkworm excrement porous carbon composite material and polybasic carboxylic acid ligand:
50 ~ 100 are mixed, and are put into autoclave and are reacted, silkworm excrement porous charcoal is obtained after then cleaning, centrifuge and drying again
MOFs composite materials.
2. the preparation method of silkworm excrement porous charcoal MOFs composite materials according to claim 1, it is characterised in that：The step
(1) silkworm excrement is 1 with water mixing plastid ratio in:100 ~ 200, mixing temperature is 30 ~ 50 o C, and incorporation time is 0.5 ~ 3 h.
3. the preparation method of silkworm excrement porous charcoal MOFs composite materials according to claim 1, it is characterised in that：The step
(1) freezing dry process is first 2 ~ 4h of precooling at -25 o o of C ~ -20 C in, is then cooled to -60 o C ~ -40
24 ~ 72h is lyophilized in o C.
4. the preparation method of silkworm excrement porous charcoal MOFs composite materials according to claim 1, it is characterised in that：Metal salt is molten
The cation of liquid is Cr3+、Fe2+Or Cu2+；Metal salt solution concentration vibrates 30 ~ 60 oC of mixing temperature in 0.1 ~ 3.0 mol/L,
6 ~ 24 h of incorporation time.
5. the preparation method of silkworm excrement porous charcoal MOFs composite materials according to claim 1, it is characterised in that：The step
(2) material and metal salt solid-liquid ratio are 1 in:50 ~ 100, it is 100 ~ 200 oC with the mixed drying temperature of metal salt solution,
Drying time is 2 ~ 12 h.
6. the preparation method of silkworm excrement porous charcoal MOFs composite materials according to claim 1, it is characterised in that：The step
(3) reaction temperature is 160 ~ 220 oC, 12 ~ 22 h of reaction time.
7. the preparation method of silkworm excrement porous charcoal MOFs composite materials according to claim 1, it is characterised in that：Polybasic carboxylic acid
Ligand is terephthalic acids or trimesic acid.
8. the preparation method of silkworm excrement porous charcoal MOFs composite materials according to claim 1, it is characterised in that：Step (1)
Middle carbonization reaming reaction temperature is 300 ~ 700 oC, and the reaction time is 0.5 ~ 5 h.
9. the material obtained by the preparation method of the silkworm excrement porous charcoal MOFs composite materials as described in claim 1 ~ 8 is any,
It is characterized in that：The material is three dimensional pore structures, and Langmuir specific surface areas are 2300 ~ 2800 m2/g。
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| 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 |
| CN105230611A (en) * | 2015-10-29 | 2016-01-13 | 仲恺农业工程学院 | Pesticide slow release agent with modified MCM-41 as carrier and preparation method thereof |
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| 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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