CN105566659A - Graphene oxide/nano cellulose aerogel and preparation method and application thereof - Google Patents
Graphene oxide/nano cellulose aerogel and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention discloses a graphene oxide/nano cellulose aerogel and a preparation method and an application thereof, and belongs to the technical field of aerogel material. The aerogel is prepared by the method including the following steps: 1) dispersing nano cellulose in hydrochloric acid to prepare a nano cellulose dispersion liquid; 2) mixing a graphene oxide dispersion liquid with the nano cellulose dispersion liquid obtained in the step 1) evenly, and carrying out a hydrothermal reaction at the temperature of 170-190 DEG C to obtain a hydrogel; and 3) carrying out freeze drying of the hydrogel obtained in the step 2) to obtain the aerogel. According to the graphene oxide/nano cellulose aerogel provided by the invention, nano cellulose and graphene oxide as raw materials are subjected to hydrothermal reaction to prepare the hydrogel, the hydrogel is further subjected to freeze drying to obtain the final product. Compared with a graphene oxide aerogel, the aerogel has better removal effect on phenol in a phenol aqueous solution, can be used for removal of organic dye molecules or other impurities in sewage, and efficiently purifies the sewage.
Description
Technical field
The invention belongs to aerogel material technical field, be specifically related to a kind of graphene oxide/nano-cellulose aerogel and its preparation method and application.
Background technology
Aerogel, that liquid original in gel removes or replaces with gas by one, thus a kind of inner bulk multi-hole obtained but do not change the special gel of some intrinsic essence such as original network structure or volume size, be hydrogel or the product of organogel by obtaining after certain method drying under certain specific condition.Aerogel material replaces liquid as dispersion medium using gas, and using solid-phase as the network skeleton of gel, its gap structure reaches Nano grade.This continuous print three-dimensional manometer network structure just makes aerogel be provided with unique performance, as high specific surface area, extremely-low density, low-k, lower thermal conductivity, unique optics and acoustical behavior etc., be therefore often applied to the fields such as wastewater treatment, catalyzer and carrier, absorption, energy storage.
Graphite oxide aerogel is mutually overlapped by a large amount of Graphene synusia, and self-assembly forms three-dimensional network shape vesicular structure.There is a large amount of holes in graphite oxide aerogel, porosity can up to 99.7%, and wherein the diameter in single hole is not from a few nanometer to several microns etc.Graphite oxide aerogel has the characteristic of hydrophobic oleophilic oil, and density is 2.4mg/cm
3graphite oxide aerogel be 0.788 ~ 1.595g/cm to density
3the saturated extent of adsorption of organic solvent up to 226 ~ 567g/g.The porous network shape structure had due to graphite oxide aerogel and the advantage of larger specific surface area, so the organic dye molecule less than graphite oxide aerogel aperture size that can contain in filtered water is got off in the effect of physical adsorption with this aerogel or other impurity, to reach the object of purifying waste water.
CN102443180A discloses a kind of method preparing cellulose composite aerogel, the method comprises: first Mierocrystalline cellulose is dissolved in sodium hydroxide/thiourea solution, sodium hydroxide/aqueous solution of urea equal solvent prepares certain density cellulose solution, and add the properties-correcting agent such as carbon nanotube (CNT), graphene oxide (GOS), redox graphene (rGO), place after making it that gelation occur and the gel obtained is carried out exchange of solvent, then, plural gel is obtained Mierocrystalline cellulose plural gel by dry.
CN103937010A discloses a kind of High-performance graphene/Mierocrystalline cellulose composite aquogel and aerogel and preparation method thereof, comprising: graphite oxide joins in ionic liquid by (1), ultrasonic disperse, obtains the solion of graphene oxide; And preparation quality number is the cellulose ionic liquid solution of 4 ~ 6wt%; (2) reductive agent is joined in graphene oxide ionic liquid solution, 80 ~ 100 DEG C, reductase 12 ~ 24h, obtain redox graphene ionic liquid mixed solution; (3) again redox graphene ionic liquid mixed solution is mixed with cellulose ionic liquid solution; (4) obtained final mixed solution is carried out deaeration, with precipitation bath regeneration, washing, obtains Graphene/Mierocrystalline cellulose composite aquogel.
In prior art, preparing Graphene/cellulose composite aerogel all needs to carry out dissolving cellulos, its complicated process of preparation with complicated ionic liquid, is difficult to realize scale operation; Focus on mechanical properties to the performance study of composite aerogel also more, other performances of aerogel material are not fully realized and are utilized.
Summary of the invention
The object of this invention is to provide a kind of graphene oxide/nano-cellulose aerogel, thus it is complicated to solve existing Graphene/cellulose composite aerogel material preparation process, cost is high, is difficult to the problem applied.
Second object of the present invention is to provide the preparation method of above-mentioned graphene oxide/nano-cellulose aerogel.
3rd object of the present invention is to provide the application of above-mentioned graphene oxide/nano-cellulose aerogel at Adsorption Organic Pollutants in Wastewater.
In order to realize above object, the technical solution adopted in the present invention is:
A kind of graphene oxide/nano-cellulose aerogel, is prepared from by the method comprised the following steps:
1) nano-cellulose is scattered in hydrochloric acid makes nano-cellulose dispersion liquid;
2) by graphene oxide dispersion and step 1) mixing of gained nano-cellulose dispersion liquid, at 170 ~ 190 DEG C, carry out hydro-thermal reaction, obtain hydrogel;
3) by step 2) gained hydrogel carries out lyophilize, to obtain final product.
Graphene oxide/nano-cellulose aerogel provided by the invention, with nano-cellulose and graphene oxide for raw material, prepares hydrogel by hydro-thermal reaction, further by lyophilize, obtains the finished product.In whole preparation process, do not use the complicated solvents such as ionic liquid, realized the compound of nano-cellulose and graphene oxide by hydro-thermal reaction, products obtained therefrom has three-dimensional network shape vesicular structure.Compared with graphite oxide aerogel, the removal effect of this aerogel Pyrogentisinic Acid phenol in aqueous solution is better, can be used for the removal of organic dye molecule or other impurity in sewage, realizes the high-efficient purification of sewage.
Step 1) in, hydrochloric acid is commercial goods, and mass concentration is 35 ~ 38%.The concentration of nano-cellulose dispersion liquid is 1 ~ 5mg/ml.The particle diameter of described nano-cellulose is 20 ~ 80nm.
Described nano-cellulose is prepared by the method comprised the following steps:
A) mixed by the vitriol oil of Microcrystalline Cellulose with mass concentration 64%, stirring reaction 60min at 40 DEG C, adds water termination reaction, obtains suspension;
B) by step a) gained suspension separation, washing, lyophilize, to obtain final product.
Described graphene oxide dispersion is that the graphite oxide obtained by hummers method is scattered in water and is prepared from.
Step 2) in, the concentration of graphene oxide dispersion is 3mg/ml.The mass ratio of graphene oxide and nano-cellulose is 45:1 ~ 5.
Step 2) in, the time of described hydro-thermal reaction is 20 ~ 25h.
Preferably, step 3) in, described cryodesiccated temperature is-50 DEG C, and pressure is 10Pa.
Preferably, the mass ratio of graphene oxide and nano-cellulose is 45:4.Hydro-thermal reaction reacts 20h at 180 DEG C.
A preparation method for graphene oxide/nano-cellulose aerogel, comprises the following steps:
1) by nano-cellulose and hydrochloric acid preparation of nano Mierocrystalline cellulose dispersion liquid;
2) by graphene oxide dispersion and step 1) mixing of gained nano-cellulose dispersion liquid, at 170 ~ 190 DEG C, carry out hydro-thermal reaction, obtain hydrogel;
3) by step 2) gained hydrogel carries out lyophilize, to obtain final product.
A kind of above-mentioned graphene oxide/nano-cellulose aerogel is in the application of Adsorption Organic Pollutants in Wastewater.Described organic pollutant is phenol.
The preparation method of graphene oxide/nano-cellulose aerogel provided by the present invention, technique is simple, and raw material is easy to get, less demanding to equipment and operator, and products obtained therefrom has broad application prospects in sewage purification, is applicable to large-scale promotion and utilizes.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of graphite (G) and graphene oxide (GO);
Fig. 2 is the infrared spectrogram of Microcrystalline Cellulose (CMC) and nano-cellulose (CNC);
Fig. 3 is the infrared spectrogram of comparative example 1 gained graphite oxide aerogel and embodiment 1 ~ 4 gained graphene oxide/nano-cellulose aerogel;
Fig. 4 is the graphite oxide aerogel of comparative example 1 and the Raman spectrum of embodiment 4 gained graphene oxide/nano-cellulose aerogel;
Fig. 5 is the TEM photo of graphene oxide; Wherein (a) is of a size of 0.2 μm, and (b) is of a size of 0.5 μm;
Fig. 6 is the SEM figure of comparative example 1 gained graphite oxide aerogel; Wherein the magnification of (a) is 100 times, and the magnification of (b) is 200 times;
Fig. 7 is the SEM figure of embodiment 4 gained graphene oxide/nano-cellulose aerogel; Wherein the magnification of (a) is 1000 times, and the magnification of (b) is 2000 times;
Fig. 8 is the canonical plotting of Adsorption of Phenol;
Fig. 9 is the adsorption curve of the graphite oxide aerogel of different add-on;
Figure 10 is the adsorption curve of embodiment 1 ~ 5 gained graphene oxide/nano-cellulose aerogel Pyrogentisinic Acid solution.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
In following examples, nano-cellulose is prepared by following steps: 10g Microcrystalline Cellulose mixes with the sulphuric acid soln of 150ml64wt% by (1), puts into heat collecting type constant-temperature heating magnetic stirring apparatus, in 40 DEG C of water-baths, react 60min; (2), after reaction terminates, the deionized water adding 10 times (1500ml) carries out dilution cooling, with termination reaction, leaves standstill; (3) solution layering after leaving standstill, outwells supernatant liquor, by nano-cellulose-sulphuric acid soln centrifugation in supercentrifuge of lower floor, removes supernatant liquor, obtains product what slurry; (4) in the centrifugal product what slurry obtained, add deionized water, carry out filtering and washing, acid free in removing solution, until pH is without considerable change, obtain nano-cellulose what slurry; (5) nano-cellulose what slurry is put into freeze drier-50 DEG C, carry out lyophilize under 10pa, obtain nano-cellulose (particle diameter is 20 ~ 80nm).
Graphene oxide dispersion is prepared by following steps: (1) is by 1g graphite, 4gKMnO
4, the 30ml vitriol oil mixes in autoclave, freezing 1.5h at 0 DEG C; (2) autoclave is put into 80 DEG C of water-baths, reaction 1.5h; (3) take out autoclave, after naturally cooling to room temperature, products therefrom (khaki color pureed) is mixed with 500ml deionized water, after magnetic agitation 15min, adds 1 ~ 3mlH
2o
2, solution colour becomes golden yellow from brown, leaves standstill 2 hours, outwells supernatant liquid, be precipitated; (4) by precipitation first wash three times with the hydrochloric acid soln of 5wt%, remove sulfate ion, then with deionized water by washing of precipitate to pH=7, centrifugal; (5) lyophilize of centrifugal gained solid is obtained graphite oxide; (6) mixed with deionized water by graphite oxide, ultrasonic vibration 1h, then magnetic agitation 0.5h, obtain graphene oxide dispersion.
Hydrochloric acid is commercial goods, and mass concentration is 35 ~ 38%.
Embodiment 1
A kind of graphene oxide/nano-cellulose aerogel, is prepared from by the method comprised the following steps:
1) nano-cellulose is scattered in hydrochloric acid makes nano-cellulose dispersion liquid; The concentration of nano-cellulose dispersion liquid is 1mg/ml;
2) by graphene oxide dispersion and step 1) mixing of gained nano-cellulose dispersion liquid, at 180 DEG C, carry out hydro-thermal reaction 20h, obtain hydrogel; The concentration of graphene oxide dispersion is 3mg/ml, and the mass ratio of graphene oxide and nano-cellulose is 45:1;
3) by step 2) gained hydrogel-50 DEG C, carry out lyophilize under 10Pa, to obtain final product.
The application of graphene oxide/nano-cellulose aerogel phenol in Adsorption phenol solution of the present embodiment.
Embodiment 2
A kind of graphene oxide/nano-cellulose aerogel, is prepared from by the method comprised the following steps:
1) nano-cellulose is scattered in hydrochloric acid makes nano-cellulose dispersion liquid; The concentration of nano-cellulose dispersion liquid is 2mg/ml;
2) by graphene oxide dispersion and step 1) mixing of gained nano-cellulose dispersion liquid, at 180 DEG C, carry out hydro-thermal reaction 20h, obtain hydrogel; The concentration of graphene oxide dispersion is 3mg/ml, and the mass ratio of graphene oxide and nano-cellulose is 45:2;
3) by step 2) gained hydrogel-50 DEG C, carry out lyophilize under 10Pa, to obtain final product.
The application of graphene oxide/nano-cellulose aerogel phenol in Adsorption phenol solution of the present embodiment.
Embodiment 3
A kind of graphene oxide/nano-cellulose aerogel, is prepared from by the method comprised the following steps:
1) nano-cellulose is scattered in hydrochloric acid makes nano-cellulose dispersion liquid; The concentration of nano-cellulose dispersion liquid is 3mg/ml;
2) by graphene oxide dispersion and step 1) mixing of gained nano-cellulose dispersion liquid, at 180 DEG C, carry out hydro-thermal reaction 20h, obtain hydrogel; The concentration of graphene oxide dispersion is 3mg/ml, and the mass ratio of graphene oxide and nano-cellulose is 45:3;
3) by step 2) gained hydrogel-50 DEG C, carry out lyophilize under 10Pa, to obtain final product.
The application of graphene oxide/nano-cellulose aerogel phenol in Adsorption phenol solution of the present embodiment.
Embodiment 4
A kind of graphene oxide/nano-cellulose aerogel, is prepared from by the method comprised the following steps:
1) nano-cellulose is scattered in hydrochloric acid makes nano-cellulose dispersion liquid; The concentration of nano-cellulose dispersion liquid is 4mg/ml;
2) by graphene oxide dispersion and step 1) mixing of gained nano-cellulose dispersion liquid, at 180 DEG C, carry out hydro-thermal reaction 20h, obtain hydrogel; The concentration of graphene oxide dispersion is 3mg/ml, and the mass ratio of graphene oxide and nano-cellulose is 45:4;
3) by step 2) gained hydrogel-50 DEG C, carry out lyophilize under 10Pa, to obtain final product.
The application of graphene oxide/nano-cellulose aerogel phenol in Adsorption phenol solution of the present embodiment.
Embodiment 5
A kind of graphene oxide/nano-cellulose aerogel, is prepared from by the method comprised the following steps:
1) nano-cellulose is scattered in hydrochloric acid makes nano-cellulose dispersion liquid; The concentration of nano-cellulose dispersion liquid is 5mg/ml;
2) by graphene oxide dispersion and step 1) mixing of gained nano-cellulose dispersion liquid, at 180 DEG C, carry out hydro-thermal reaction 20h, obtain hydrogel; The concentration of graphene oxide dispersion is 3mg/ml, and the mass ratio of graphene oxide and nano-cellulose is 45:5;
3) by step 2) gained hydrogel-50 DEG C, carry out lyophilize under 10Pa, to obtain final product.
The application of graphene oxide/nano-cellulose aerogel phenol in Adsorption phenol solution of the present embodiment.
Comparative example 1
This comparative example prepares graphite oxide aerogel, and preparation process comprises: the graphite oxide dispersion 15ml getting 3mg/ml joins in autoclave, hydrothermal treatment consists 20 hours in the baking oven of 180 DEG C.After hydrothermal treatment consists, by autoclave naturally cooling, pour out product ,-50 DEG C, under 10Pa lyophilize obtain graphite oxide aerogel.
Test example 1
This test example utilizes the structure of infrared spectra (FT-IR) to embodiment gained graphene oxide/nano-cellulose aerogel to characterize.
Fig. 1 is the infrared spectrogram of graphite (G) and graphene oxide (GO).As can be seen from the figure, graphene oxide is at 3430cm
-1near have wider, a stronger absorption peak, this is the stretching vibration peak belonging to-OH; At 1725cm
-1place is the stretching vibration peak of the C=O of the carboxyl of graphene oxide; At 1630cm
-1the absorption peak at place is the flexural vibration peak belonging to C-OH; At 1110cm
-1the absorption peak-to-peak at place is the stretching vibration peak of C-O-C, illustrates that the graphene oxide of preparation at least exists-OH ,-COOH, C-O-C ,-C=O four functional groups.The existence of these group characteristic peaks illustrates graphite oxidation success, due to the effect of these polar groups, makes graphene oxide be easy to form hydrogen bond with water molecules, and then explains graphene oxide and have good hydrophilic reason.
Fig. 2 is the infrared spectrogram of Microcrystalline Cellulose (CMC) and nano-cellulose (CNC); As can be seen from the figure the figure tendency of the two does not change substantially, and the change of just size is described, does not generate other chemical bond or the change of generation chemical structure.3379cm
-1for the stretching vibration peak of-OH, 2900cm
-1place is CH
2symmetrical absorption peak, 1610cm
-1place is the stretching vibration absorption peak of C=O, 1430cm
-1for-CH
3flexural vibration absorption peak, 1372cm
-1place is CH in-plane bending vibration absorption peak, 1111cm
-1place is the stretching vibration absorption peak of C-O, 665cm
-1place is C-H out-of-plane bending absorption peak.
Fig. 3 is the infrared spectrogram of comparative example 1 gained graphite oxide aerogel and embodiment 1 ~ 4 gained graphene oxide/nano-cellulose aerogel; 1381cm
-1the O-H flexural vibration absorption peak at place is moved to 1406cm by high frequency
-1, 2918cm
-1the CH at place
2stretching vibration peak is moved to 2924cm to high frequency
-1, and the absorption peak of embodiment 1 is the strongest; In the infared spectrum of embodiment 3, each characteristic peak is sharp-pointed; Can find out, the chemical structure of each embodiment gained graphene oxide/nano-cellulose aerogel is substantially identical.
Test example 2
The crystalline structure of this test example to the graphite oxide aerogel of comparative example and embodiment 4 gained graphene oxide/nano-cellulose aerogel detects, and Fig. 4 is its Raman spectrum.As seen from the figure, (C=C key, comes from sp for D-bands of a spectrum (C-C key comes from unordered graphite-structure) and G-bands of a spectrum
2hydridization carbon structure) lay respectively at 1356cm
-1and 1579cm
-1place.Aerogel D-bands of a spectrum displacement after graphene oxide and nano-cellulose compound 7cm
-1, G-bands of a spectrum displacements 8cm
-1.In addition, according to the peak area (R=I of D-bands of a spectrum and G-bands of a spectrum
d/ I
g) degree of the order and disorder of carbon atom on carbon material, the I of comparative example graphite oxide aerogel can be judged
d/ I
gvalue is 1.22, the I of graphene oxide/nano-cellulose aerogel prepared by embodiment
d/ I
gvalue is 1.27.It has been generally acknowledged that displacement and the I of Raman spectrum
d/ I
gthe rising of value is due to sp in face
2ordered graphitic crystalline structure is destroyed and causes in the reduction of area size and functionalization process.This also ascribes between Graphene and polymkeric substance exists interactional result.In fact, containing a large amount of hydroxyls and carboxylic group on graphene oxide molecular chain, and cellulose molecular chain also has abundant containing oxygen group, be very easy to the Intermolecular Forces forming hydrogen bond and so between the two.This also just composite aerogel be adsorbed with organic pollutants effect strengthen reason.
Test example 3
The surface topography of this test example to the graphite oxide aerogel of comparative example and embodiment 4 gained graphene oxide/nano-cellulose aerogel is observed.
Fig. 5 is the TEM photo of graphene oxide; A () is of a size of 0.2 μm, (b) is of a size of 0.5 μm; As can be seen from the figure graphene oxide presents transparent tulle shape, simultaneously show obvious wavy fold in surface of graphene oxide, this may be that oxygen-containing functional group owing to introducing between graphene sheet layer makes the reaction force attenuation between lamella cause.
Fig. 6 is the SEM figure of comparative example 1 gained graphite oxide aerogel; Wherein the magnification of (a) is 100 times, and the magnification of (b) is 200 times; As can be seen from the figure graphite oxide aerogel is overlapped mutually by a large amount of graphene oxide synusia, and self-assembly forms three-dimensional network shape vesicular structure, and the diameter in hole differs.
Fig. 7 is the SEM figure of embodiment 4 gained graphene oxide/nano-cellulose aerogel; Wherein the magnification of (a) is 1000 times, and the magnification of (b) is 2000 times; Can find out that the form of this aerogel is irregular spherical from figure (a), and concentrate in together into tufted, indistinctly can find out and have hole to be mixed in wherein, very clearly can see that the hole having a lot of diameter to differ exists from figure (b).
Test example 4
The adsorption effect of this test example to each embodiment and the comparative example gained aerogel Pyrogentisinic Acid aqueous solution detects.In this test example, adopt quinizine spectrophotometry to carry out Pyrogentisinic Acid and carry out analysis mensuration.Using the Tripotassium iron hexacyanide as developer under slight alkalinity condition, measure absorbancy at wavelength 510nm place, determine the residual concentration of Phenol in Aqueous Solution thus.
In testing process, each reagent prepares as follows:
Phenol Standard storing solution: accurately take colourless phenol solid 0.5g and be placed in beaker, add a certain amount of deionized water to be dissolved, obtain phenol solution, then transferred in 500ml volumetric flask, be settled to 500ml, be made into the phenol colourless solution that concentration is 1mg/mL.The phenol solution getting 5ml with transfer pipet, in the volumetric flask of 100ml, is diluted to scale marks with deionized water, is configured to the phenol solution of 50 μ g/ml, for subsequent use.
Ammonia buffer: accurately take 2gNH
4cl white powder, is dissolved in the ammoniacal liquor of 100ml, is mixed with the ammonia buffer of pH ≈ 10, wraps with preservative film, put into refrigerator, for subsequent use.
4-AA solution: take the faint yellow 4-AA pressed powder of 2g and be put in beaker, add a certain amount of deionized water, dissolved, then solution is transferred in the volumetric flask of 100ml, be settled to scale marks, be made into the pale yellow solution that mass concentration is 2%, put into refrigerator, for subsequent use.
Potassium ferricyanide solution: take 8g Tripotassium iron hexacyanide red granules, be put in beaker, the deionized water adding 92ml is dissolved, is made into the potassium ferricyanide solution that mass concentration is 8%, puts into refrigerator, for subsequent use.
The drafting of typical curve adopts following methods: a peek 25mL color-comparison tube, respectively to wherein add 50 μ g/ml phenol solution 0.50,1.00,3.00,5.00,8.00,10.00,15.00,20.00mL, appropriate amount of deionized water is added in colorimetric cylinder, in colorimetric cylinder, add ammonia buffer 0.25ml with transfer pipet again, mix; In colorimetric cylinder, add the 4-AA solution of 0.5ml again with transfer pipet, mix; In colorimetric cylinder, add potassium ferricyanide solution 0.5ml with transfer pipet again, mix; Then deionized water is to 25ml scale marks, is finally diluted one times with 25ml deionized water again, places.After 20min, utilizing ultraviolet spectrophotometer, take blank solution as reference, measures absorbancy, is recorded in the absorbancy of solution during 510nm place.
Employing formula (1) and formula (2) calculate adsorptive capacity and the adsorption efficiency of aerogel Pyrogentisinic Acid.
In formula (1), formula (2), Q is the adsorptive capacity (mg/g) of sorbent material; C
0for the starting point concentration (mg/mL) of phenol solution; C is the residual concentration (mg/mL) of phenol solution; M is the quality (mg) of sorbent material.
Adsorption test flow process is as follows: the aerogel accurately taking 2mg, puts into 100mL tool plug Erlenmeyer flask, then in Erlenmeyer flask, adds phenol Standard solution 45mL.Place it on shaking table, in certain temperature, vibrate under certain rotating speed, take out after 1 hour, centrifugation is carried out to suspension, the supernatant liquor pipetting 5ml is placed in the colorimetric cylinder of 25ml, add ammonia damping fluid 0.25ml wherein successively, 4-AA solution 0.5ml, potassium ferricyanide solution 0.5ml, then deionized water is added to 25ml scale marks, mix, last 25ml deionized water of using again is diluted one times, leave standstill 15min, the absorbancy of phenol is measured with ultraviolet-visible pectrophotometer, compare with typical curve, calculate residual phenol concentration.Adsorptive capacity and adsorption efficiency can be calculated by formula (1) and formula (2).
Table 1 is the test data of phenol content and absorbancy, and with the content of phenol for X-coordinate, absorbancy is ordinate zou, drawing standard defect, as shown in Figure 8.Can find out between absorbancy and phenol concentration, to there is good linear relationship, linearly dependent coefficient R
2=0.9984, it is y=0.0027x-0.04551 that linear matching obtains straight-line equation.
The relation of table 1 phenol amount and absorbancy
Fig. 9 is the adsorption curve of the graphite oxide aerogel (comparative example 1 gained) of different add-on.As can be seen from the figure when the amount of the GO aerogel added is 1mg, adsorption efficiency is 19.8%, and when the amount of GO aerogel is 2mg, adsorption efficiency is 28.3%, and when the amount of GO aerogel is 6mg, the adsorption effect of Pyrogentisinic Acid is best, and adsorption efficiency is 34.1%.When 2mg, adsorption efficiency change is maximum, therefore selects the subsequent adsorbtion of the graphene oxide/nano-cellulose aerogel of embodiment 1 ~ 5 test add-on to be 2mg.
Figure 10 is the adsorption curve of embodiment 1 ~ 5 gained graphene oxide/nano-cellulose aerogel Pyrogentisinic Acid solution.As can be seen from the figure, the adsorption efficiency of each embodiment gained aerogel is all higher than the adsorption efficiency of comparative example gained graphite oxide aerogel, and the adsorption effect of embodiment 4 gained aerogel Pyrogentisinic Acid is best, reaches 38.2%.
Claims (9)
1. graphene oxide/nano-cellulose aerogel, is characterized in that, is prepared from by the method comprised the following steps:
1) nano-cellulose is scattered in hydrochloric acid makes nano-cellulose dispersion liquid;
2) by graphene oxide dispersion and step 1) mixing of gained nano-cellulose dispersion liquid, at 170 ~ 190 DEG C, carry out hydro-thermal reaction, obtain hydrogel;
3) by step 2) gained hydrogel carries out lyophilize, to obtain final product.
2. graphene oxide/nano-cellulose aerogel as claimed in claim 1, is characterized in that, step 1) in, the concentration of nano-cellulose dispersion liquid is 1 ~ 5mg/ml.
3. graphene oxide/nano-cellulose aerogel as claimed in claim 1, is characterized in that, step 2) in, the concentration of graphene oxide dispersion is 3mg/ml.
4. graphene oxide/nano-cellulose aerogel as claimed in claim 1, is characterized in that, step 2) in, the mass ratio of graphene oxide and nano-cellulose is 45:1 ~ 5.
5. graphene oxide/nano-cellulose aerogel as claimed in claim 1, is characterized in that, step 2) in, the time of described hydro-thermal reaction is 20 ~ 25h.
6. graphene oxide/nano-cellulose aerogel as claimed in claim 1, is characterized in that, step 3) in, described cryodesiccated temperature is-50 DEG C, and pressure is 10Pa.
7. graphene oxide/the nano-cellulose aerogel as described in any one of claim 1 ~ 6, is characterized in that, described nano-cellulose is prepared by the method comprised the following steps:
1) mixed by the vitriol oil of Microcrystalline Cellulose with mass concentration 64%, stirring reaction 60min at 40 DEG C, adds water termination reaction, obtains suspension;
2) by step 2) separation of gained suspension, washing, lyophilize, to obtain final product.
8. a preparation method for graphene oxide/nano-cellulose aerogel, is characterized in that, comprises the following steps:
1) nano-cellulose is scattered in hydrochloric acid makes nano-cellulose dispersion liquid;
2) by graphene oxide dispersion and step 1) mixing of gained nano-cellulose dispersion liquid, at 170 ~ 190 DEG C, carry out hydro-thermal reaction, obtain hydrogel;
3) by step 2) gained hydrogel carries out lyophilize, to obtain final product.
9. graphene oxide/nano-cellulose aerogel as claimed in claim 1 is in the application of Adsorption Organic Pollutants in Wastewater.
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