CN103785364A - Graphene-metal-poly(m-phenylenediamine) plural gel as well as quick preparation and application methods thereof - Google Patents

Graphene-metal-poly(m-phenylenediamine) plural gel as well as quick preparation and application methods thereof Download PDF

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CN103785364A
CN103785364A CN201410068005.8A CN201410068005A CN103785364A CN 103785364 A CN103785364 A CN 103785364A CN 201410068005 A CN201410068005 A CN 201410068005A CN 103785364 A CN103785364 A CN 103785364A
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graphene
metal
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phenylene diamine
gel
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CN103785364B (en
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王海鹰
柴立元
王婷
张理源
杨卫春
杨志辉
唐崇俭
刘恢
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Central South University
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Abstract

The invention discloses graphene-metal-poly(m-phenylenediamine) plural gel as well as quick preparation and application methods thereof. In the method, metal ions, organic monomers and graphene oxide are taken as raw materials, a high-activity complex comprises the metal ions and the organic monomers, and the graphene-metal-poly(m-phenylenediamine) plural gel is obtained by performing in-situ reduction oxidation on graphite so as to cause graphene gelatinization and then performing one-step quick hydrothermal. According to the method, the redox characteristics of the raw materials are fully used, so that a polymerization initiator and a gel crosslinking agent do not need to be added; the preparation method is simple and fast (1-2 hours); the monomer conversion rate is higher than or equal to 99.0 percent; the synthesis process is clean, and the cost is low; the plural gel can be used for high-efficiency dye adsorption; the static saturated adsorption (methylthionine chloride) capacity is up to 615mg/g<-1>.

Description

A kind of Graphene-metal-poly m-phenylene diamine plural gel and fast methods for making and using same
Technical field
The invention belongs to the preparation of Graphene plural gel and water treatment field thereof, relate to clean quick synthetic Graphene composite gel material of an a kind of step and preparation method thereof, and use it for the application process of water body Dye Adsorption.
Background technology
Hydrogel, is the flexible macro-size body of a class, is widely used in the basic research fields such as energy storage, catalysis, biological medicine, environment.(Chemical Society Reviews2013,42 (2), 794-830; Chemical Society Reviews2010,39 (9), 3528-3540) relating to the environmental area of adsorption process, its advantage outstanding behaviours is: 1) microcosmic loose structure is given its excellent mass-transfer efficiency, is conducive to pollutant and quickly diffuses to avtive spot; 2) macroscopical three-dimensional structure has solved the problem of the loaded down with trivial details separation of nano-component; 3) can be according to application purpose by organic element assembling, thus multifunctional composite can be obtained.But be in difficult point and the key of environmental area based on hydrogel, exploitation rapid and convenient obtains the preparation method who stablizes hydrogel, and high performance target adsorbent is assembled into three-dimensional macro size body.
At present, the charcoal hydrogel preparation research that is raw material based on Graphene is extensive.Graphene is a kind of conjugation material with carbon element with two dimensional surface microstructure, and specific area is large, is the ideal element of constructing gel.(Small2013,9 (8), 1397 – 1404; Advanced Materials2014,26 (4), 615-619) but single charcoal hydrogel exists avtive spot limited, the defects such as functional group is few, introduce function ingredients (as being rich in the organic polymer etc. of functional group) synthesizing graphite alkene compound gel, can effectively even produce special cooperative effect in conjunction with the advantage of different component, greatly promote application performance, become the study hotspot in current this field.（Advanced?Materials2014,26(4),615-619；Journal?of?Applied?Polymer?Science2014,131(3)；Chemical?Communications2013,49(85),9974-9976；）
Graphene polymer becomes gel mechanism mainly to comprise: after graphite oxide reduction crosslinked (covalency, static or π-π effect) of hydrophobic effect, polymer.Therefore in Graphene polymer gel preparation process, often need to add reducing agent (NaBH 4, HI, Na 2s, hydroquinones, ascorbic acid etc.) (Nanoscale2011,3 (8), 3132-3137; Journal of Materials Chemistry2012,22 (42), 22459-22466), crosslinking agent (Ca 2+, PAM) (Small2013,10 (3), 448 – 453), polymerization initiator ((NH 4) 2s 2o 8) (2013,25 (16), 3357-3362) or pre-synthesis step (the Chemical Communications2013 of polymer, 49 (85), 9974-9976) etc., and reaction condition is relatively harsh, as requires the steps such as high temperature hydro-thermal (t>=6h), building-up process relative complex and easily cause secondary pollution (polymer building-up process residual toxicity monomer).Therefore, the novel preparation method of exploitation one class, significant with rapid cleaning synthesizing graphite alkene class plural gel.
Summary of the invention
The object of this invention is to provide a kind of gentle, without adding under redox reagent condition, the method for the quick synthesizing graphite alkene plural gel of a step, and the plural gel for preparing of the method and its application process.
Target of the present invention realizes by the following method.
A preparation method for Graphene-metal-poly m-phenylene diamine plural gel, mixes metal ion with organic monomer, form metal-organic monomer high activity complex, and then in-situ reducing rapid induction graphene oxide are prepared gel.
Described metal ion comprises copper ion and iron ion; Described organic monomer comprises: m-phenylene diamine (MPD).
The preparation method of described Graphene-metal-poly m-phenylene diamine plural gel specifically first mixes metal salt solution with m-phenylene diamine (MPD) solution, solution is transformed into rapidly dark-brown, form metal-organic monomer high activity complex, rapidly complex is added in graphene oxide solution and mixed again, the gelation of enzymatic oxidation Graphene-metal-poly m-phenylene diamine, through hydro-thermal reaction, obtain Graphene-metal-poly m-phenylene diamine plural gel.
The preparation method of above-mentioned Graphene-metal-poly m-phenylene diamine plural gel, it is the graphene oxide solution of 2-20mg/mL that complex is added to concentration.
The preparation method of above-mentioned Graphene-metal-poly m-phenylene diamine plural gel, complex is added in graphene oxide solution and mixed, the mass percent that slaine accounts for overall reaction system is 5%-25%, and the mass percent that m-phenylene diamine (MPD) accounts for overall reaction system is 10%-40%.
The preparation method of above-mentioned Graphene-metal-poly m-phenylene diamine plural gel, is first that the m-phenylene diamine (MPD) solution that 5-50mg/L metal salt solution is 5-30mg/L with concentration mixes by concentration, forms metal-organic monomer high activity complex.
The preparation method of above-mentioned Graphene-metal-poly m-phenylene diamine plural gel, complex adds in graphene oxide solution fast, ultrasonic lower mixing 0.5-5min.
The preparation method of above-mentioned Graphene-metal-poly m-phenylene diamine plural gel, the temperature of hydro-thermal reaction is 80-95 ℃, the time is 1-2h.
A kind of Graphene-metal-poly m-phenylene diamine plural gel is to be prepared from by above-mentioned method.
The application process of above-mentioned Graphene-metal-poly m-phenylene diamine plural gel is to adopt absorption method to remove water body dyestuff.
The preparation method of Graphene-metal of the present invention-poly m-phenylene diamine gel, it is the high activity ligand forming based on metal-organic monomer, thereby realize self-polymerization, redox graphene, the gelation of in-situ cross-linked initiation Graphene, a step is the synthetic graphene complex gel with three-dimensional netted skeleton structure fast.
Graphene-metal of the present invention-poly m-phenylene diamine gel, adopts dynamic adsorption method to remove water body dyestuff.Concrete grammar is the synthetic gel matching with adsorption column size, and gel is put into absorption cylinder, is 10mg L toward wherein adding initial concentration -1dyestuff, penetration speed is 20L m -2h -1-180L m -2h -1, under this experiment condition, Dynamic Adsorption 200mL dyestuff, clearance>=90%; Static saturated adsorption capacity is up to 615mg g -1.
Beneficial effect of the present invention:
(1) in Graphene plural gel synthetic method provided by the invention; metal ion plays the double action of catalytic polymerization, cross-linked gel; organic monomer is born the function of reducing agent, gel crosslinking agent, and graphene oxide is as oxidant and three-dimensional structure module units.Reaction is fast efficient, without extra conventional polymeric initator, the reductant-oxidant of adding, avoids prepolymerization step, only 1h of hydro-thermal time, and monomer conversion reaches more than 99.0%, and building-up process reaction efficiency is high, simple to operate, and clean friendly, cost is low.
(2) gained hydrogel material of the present invention has good mechanical property, and product structure is stable, and highly for the gel maximum compressive strength of 1cm can reach 0.1MPa, can bear is highly 100 times of 1m(oneself height) water column.
(3) plural gel that the present invention obtains, has macro-size, is easy to separate, and is rich in duct on microcosmic, not only guaranteed efficient mass transfer efficiency but also solved conventional nano adsorber separate loaded down with trivial details, easily residual, there is the problems such as secondary harm.Gained gel specific area reaches 337.3m 2g -1, there is excellent Dye Adsorption performance, dynamically saturated adsorption 200mL initial concentration is 10mgL -1methylene blue, clearance>=90%; Static Adsorption methylene blue saturated extent of adsorption is up to 615mg g -1, be better than the carbon back sorbing material of bibliographical information.
Accompanying drawing explanation:
Fig. 1 is SEM figure, pictorial diagram and the mechanical performance figure of gel in embodiment 1;
Fig. 2 is that in embodiment 6, gel is schemed for methylene blue Dynamic Adsorption (A) and Static Adsorption performance (B).
The specific embodiment
With specific embodiment, the preparation method of the Graphene-metal-polymer in the present invention is described below and is applied to the method for Dye Adsorption, and can not form limitation of the present invention.
Embodiment 1: synthesizing graphite alkene-copper-poly m-phenylene diamine gel.
5g graphite powder is slowly added under ice bath to 30g KMnO 4and in the mixed solution of the 120mL concentrated sulfuric acid, after stirring, be warming up to 35 ℃ of reaction 30min, and add after 500mL water and heat up 85 ℃ and react 2h, add while hot 200mL30%H 2o 2, fully suction filtration, dialysis are to remove foreign ion, and product is graphene oxide.Be 5mg mL by 5ml concentration -1the ultrasonic dispersion of graphene oxide 1h, obtain graphene oxide uniform dispersion.Be 10mg mL by 1mL concentration -1m-phenylene diamine (MPD) solution and 0.1mL concentration be 40mg mL -1cuCl 22H 2o solution mixes, and ultrasonic lower adding rapidly in graphene oxide dispersion liquid, forms GO-Cu-mPD gel (t≤1min).By 95 ℃ of reaction 1h of this gel, obtain rGO-Cu-PmPD gel.By measuring the residual solution content of organic matter (TOC method), metal ion content (atomic absorption method), assessment monomer conversion ratio, metal ion-chelant rate, result shows that monomer conversion is up to 99.3%, metal ion-chelant rate is 95.3%.After gained gel refrigeration drying, recording specific area is 337.3m 2g -1, Fig. 1 is material object, SEM and the mechanical performance figure of gained gel, and result shows that gel is cellular, and hydrogel maximum compressive strength can reach 0.1MPa.
Embodiment 2: synthesizing graphite alkene-copper-poly m-phenylene diamine gel.
The preparation of graphene oxide is with embodiment 1.Be 2mg mL by 5ml concentration -1the ultrasonic dispersion of graphene oxide 1h, obtain graphene oxide uniform dispersion.Be 10mg mL by 1mL concentration -1m-phenylene diamine (MPD) solution and 0.1mL concentration be 40mgmL -1cuCl 22H 2o solution mixes, ultrasonic lower adding rapidly in graphene oxide dispersion liquid.Leave standstill 1min, form GO-Cu-mPD gel, by 90 ℃ of reaction 1h of this gel, obtain rGO-Cu-PmPD gel.Monomer conversion is up to 99.5%, and metal ion-chelant rate is 94.7%.
Embodiment 3: synthesizing graphite alkene-copper-poly m-phenylene diamine gel.
The preparation of graphene oxide is with embodiment 1.Be 5mg mL by 5ml concentration -1the ultrasonic dispersion of graphene oxide 1h, obtain graphene oxide uniform dispersion.Be 20mg mL by 1mL concentration -1m-phenylene diamine (MPD) solution and 0.2mL concentration be 40mgmL -1cuCl 22H 2o solution mixes, ultrasonic lower adding rapidly in graphene oxide dispersion liquid.Leave standstill 1min, form GO-Cu-mPD gel, by 80 ℃ of reaction 2h of this gel, obtain rGO-Cu-PmPD gel.Monomer conversion is up to 99.1%, and metal ion-chelant rate is 92.9%
Embodiment 4: synthesizing graphite alkene-iron-poly m-phenylene diamine gel.
The preparation of graphene oxide is with embodiment 1.Be 5mg mL by 5ml concentration -1the ultrasonic dispersion of graphene oxide 1h, obtain graphene oxide uniform dispersion.Be 10mg mL by 1mL concentration -1m-phenylene diamine (MPD) solution and 0.1mL concentration be 50mgmL -1feCl 36H 2o(pH is 3) solution mixing, ultrasonic lower adding rapidly in graphene oxide dispersion liquid.Leave standstill 1min, form GO-Fe-mPD gel, by 80 ℃ of reaction 2h of this gel, obtain rGO-Fe-PmPD gel.Monomer conversion is up to 99.4%, and metal ion-chelant rate is 93.2%.
Embodiment 5: synthesizing graphite alkene-iron-poly m-phenylene diamine gel.
The preparation of graphene oxide is with embodiment 1.Be 5mg mL by 5ml concentration -1the ultrasonic dispersion of graphene oxide 1h, obtain graphene oxide uniform dispersion.Be 10mg mL by 1mL concentration -1m-phenylene diamine (MPD) solution and 0.3mL concentration be 50mgmL -1feCl 36H 2o(pH is 3) solution mixing 5s, add in graphene oxide dispersion liquid under ultrasonic.Leave standstill 1min, form GO-Fe-mPD gel, by 95 ℃ of reaction 1h of this gel, obtain rGO-Fe-PmPD gel.Monomer conversion is up to 99.3%, and metal ion-chelant rate is 91.5%.
Embodiment 6: the gel-filled post of Graphene-copper-poly m-phenylene diamine is for methylene blue Dynamic Adsorption.
The adsorption column (the initial material gross mass of gel: 20mg) of gel (synthetic according to proportioning in embodiment 1) will be housed, for simulating post absorption.Initial methylene blue solution concentration is 10mg L -1, be 50L m by air-flow control method control dyestuff penetration speed -2h -1, every 10mL gets a little, adopts UV-vis to measure residual methylene blue concentration, filters with this understanding 200mL dyestuff, still can realize clearance>=90%.In this example, equilibrium adsorption capacity is 150mg g -1.
Embodiment 7: Graphene-copper-poly m-phenylene diamine gel is for methylene blue Static Adsorption.
Proportioning in embodiment 1 is reacted to the gel obtaining, be ultrasonicly scattered in (ultrasonic 5min) in methylene blue solution, methylene blue solution initial concentration scope is 20-300mg L -1, controlling temperature is 25 ℃, stirs 12h, adopts UV-vis to measure residual methylene blue concentration after isolated by filtration, in this condition, gel saturated extent of adsorption is 615mg g -1, higher than document relevant report value, contrast in table 1 with same type of material absorption property in document.
The absorption property contrast of table 1 carbon-bearing adsorbent to methylene blue
Figure BDA0000470391960000051

Claims (10)

1. a preparation method for Graphene-metal-poly m-phenylene diamine plural gel, is characterized in that, metal ion is mixed with organic monomer, forms metal-organic monomer high activity complex, and then in-situ reducing rapid induction graphene oxide are prepared gel.
2. the preparation method of Graphene-metal according to claim 1-poly m-phenylene diamine plural gel, is characterized in that, described metal ion comprises copper ion and iron ion; Described organic monomer comprises: m-phenylene diamine (MPD).
3. the preparation method of Graphene-metal according to claim 1-poly m-phenylene diamine plural gel, it is characterized in that, first metal salt solution is mixed with m-phenylene diamine (MPD) solution, solution is transformed into rapidly dark-brown, form metal-organic monomer high activity complex, more rapidly complex is added in graphene oxide solution and mixed, the gelation of enzymatic oxidation Graphene-metal-poly m-phenylene diamine, through hydro-thermal reaction, obtain Graphene-metal-poly m-phenylene diamine plural gel.
4. the preparation method of Graphene-metal according to claim 3-poly m-phenylene diamine plural gel, is characterized in that, it is the graphene oxide solution of 2-20mg/mL that complex is added to concentration.
5. the preparation method of Graphene-metal according to claim 4-poly m-phenylene diamine plural gel, it is characterized in that, complex is added in graphene oxide solution and mixed, the mass percent that slaine accounts for overall reaction system is 5%-25%, and the mass percent that m-phenylene diamine (MPD) accounts for overall reaction system is 10%-40%.
6. the preparation method of Graphene-metal according to claim 3-poly m-phenylene diamine plural gel, it is characterized in that, be first that the m-phenylene diamine (MPD) solution that 5-50mg/L metal salt solution is 5-30mg/L with concentration mixes by concentration, form metal-organic monomer high activity complex.
7. the preparation method of Graphene-metal according to claim 3-poly m-phenylene diamine plural gel, is characterized in that, complex adds in graphene oxide solution fast, ultrasonic lower mixing 0.5-5min.
8. the preparation method of Graphene-metal according to claim 3-poly m-phenylene diamine plural gel, is characterized in that, the temperature of hydro-thermal reaction is 80-95 ℃, and the time is 1-2h.
9. Graphene-metal-poly m-phenylene diamine plural gel, is characterized in that, is to be prepared from by the method described in claim 1-8 any one.
10. the application process of Graphene-metal claimed in claim 9-poly m-phenylene diamine plural gel, is characterized in that, is to adopt absorption method to remove water body dyestuff.
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CN106082202A (en) * 2016-06-29 2016-11-09 北京化工大学 A kind of preparation method and application of graphene aerogel
CN109517211A (en) * 2018-09-28 2019-03-26 浙江工业大学 A kind of amino porous polymer and the preparation method and application thereof

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CN104071785A (en) * 2014-07-14 2014-10-01 中国科学院福建物质结构研究所 Method for preparing graphene with three-dimensional macroscopic porous structure
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CN104558598A (en) * 2015-01-04 2015-04-29 常州大学 One-step method for synthesizing poly(m-phenylenediamine) and graphene composite material and application of composite material to electric adsorption of heavy metal ions in water
CN106082202A (en) * 2016-06-29 2016-11-09 北京化工大学 A kind of preparation method and application of graphene aerogel
CN106082202B (en) * 2016-06-29 2018-07-27 北京化工大学 A kind of preparation method and application of graphene aerogel
CN109517211A (en) * 2018-09-28 2019-03-26 浙江工业大学 A kind of amino porous polymer and the preparation method and application thereof

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