CN109529776A - A kind of graphene oxide-ceric hydroxide composite material, preparation method and applications - Google Patents
A kind of graphene oxide-ceric hydroxide composite material, preparation method and applications Download PDFInfo
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- CN109529776A CN109529776A CN201910048216.8A CN201910048216A CN109529776A CN 109529776 A CN109529776 A CN 109529776A CN 201910048216 A CN201910048216 A CN 201910048216A CN 109529776 A CN109529776 A CN 109529776A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of graphene oxide-ceric hydroxide composite materials, preparation method and applications.This experiment prepares graphene oxide-ceric hydroxide composite material (Ce (OH) by direct precipitation method and hydrothermal synthesis method4/ GO) Congo red (CR) and phosphate anion (PO in solution are adsorbed and removed with it4 3‑), and characterized by the structure to composite material such as SEM, FT-IR, by under the conditions ofs different pH, temperature and initial mass concentration etc. to Congo red (CR) and phosphate anion (PO4 3‑) adsorption effect inquired into, it is determined that optimal adsorption condition be respectively as follows: pH be 7.0 and 6.0, adsorption time be 6 hours, temperature be 50 DEG C and 30 DEG C.Congo red and PO is obtained by Langmuir model analysis4 3‑Maximal absorptive capacity be respectively 563.67mg/g, 619.63mg/g, adsorption effect is significant.
Description
[technical field]
The invention belongs to water treatment agent preparation technical fields, and in particular to a kind of graphene oxide-ceric hydroxide is compound
Material, preparation method and applications.
[background technique]
There are many wastewater processing technologies, such as: flocculation, film filtering, solvent extraction, biological adsorption, chemical precipitation, ion are handed over
It changes, inverse osmosis, electrocoagulation, sintering, electrodeposit method, coagulation and absorption method etc..Wherein absorption method is to produce cheap and behaviour
Deal with the method that the simple advantage of process has become the removal pollutant being widely used, the excellent novel suction of design adsorption capacity
Attached dose seems extremely important.
There are many adsorbent species, can be divided mainly into 3 classes:
The first kind is for more typical porous adsorbing material, such as active carbon, zeolite and absorption resin.
Second class is non-porous adsorbent material, and this kind of material is studied less at present, mainly (such as: glass including fibrous material
Fiber, cotton fiber and chemical fibre etc.), biomaterial (including algae, chitosan, mycelium and activated sludge etc.) and mineral
Material (such as kaolin, magnetic iron ore).
Third class is nano adsorption material, since nano adsorption material usually has biggish specific surface area and good table
Face adsorption activity, so it has become the research focus of environmentalist in recent years.Most study is carbon nanometer at present
Pipe, (oxidation) graphene, fullerene, titania nanotube etc..
A kind of two-dimensional material of the graphene oxide as novel single layer of carbon atom thickness, table Qu Fuhan various active base
Group mainly includes the oxygen-containing functional groups such as a large amount of hydroxyl, carboxyl, epoxy group in its surface, the presence of these active oxygen-containing groups
Necessary adsorption site can be provided for pollutant, greatly improve the dissolubility of GO, can effectively avoid reuniting
Phenomenon, and GO essentially consists in the active force occurred between its zwitterion to the adsorption capacity of various dyestuffs and metal ion, institute
There is superior absorption property with GO, in processing waste water from dyestuff with very big application prospect, but the graphite oxide after adsorbing
Alkene will be dissolved in water, and be difficult to extract from solvent, cannot be reused, cause significant wastage.
So the novel oxidized graphene-based metallic compound composite material adsorbent that invention can be recycled becomes new hot spot.
Synthesized a variety of (oxidations) graphene-based metallic compound nano material so far, including with TiO2、
ZnO、MnO2、CeO2、Fe3O4、Zn-Fe3O4、Ag3PO4、Bi2WO6Equal composite materials.It is multiple to synthesize graphene oxide-rare earth compound
Condensation material is also more rare as adsorbent.The method of direct precipitation method is most common preparation method.Using including colloidal sol one
The methods of the hot method of gel method, hydrothermal/solvent, electrochemical deposition, microwave-assisted growth prepare one metal oxygen of graphene oxide
Compound composite material also achieves good results.
Cerium is a kind of silver-gray active metal, and powder easy spontaneous combustion in air is soluble in acid, the abundance in rare earth element
Highest.As alloy addition, reducing agent, and for producing cerium salt etc., it is also used for the industry such as medicine, process hides, glass, weaving.
Cerium oxide is that yellowish or yellowish-brown helps powder.Density 7.13g/cm3.2397 DEG C of fusing point.Not soluble in water and alkali, is slightly soluble in acid,
Performance is to do polishing material, catalyst, catalyst carrier (auxiliary agent), ultraviolet absorbing agent, fuel-cell electrolyte, vehicle exhaust
Absorbent, electronic ceramics etc..
In conclusion the metallic compound of graphite oxide alkenes composite material adsorbent load is mainly ZnO, MnO2、
CeO2、Fe3O4Deng having not seen load C e (OH)4Report.The magnetic adsorbent that the rare-earth adsorbent having been reported that mainly has
(Fe304@Y(OH)CO3With Fe304@CeO2.nH20) and rare earth lanthanum oxide is carried on zeolite etc., but not with graphene oxide knot
It closes.It will lead to rare earth compound in this way and agglomeration occur, specific surface area reduces, and causes adsorption site to reduce, adsorption effect is remote
Lower than rare earth compound uniform load in the effect for generating synergistic effect on graphene oxide.
[summary of the invention]
The present invention provides a kind of graphene oxide-ceric hydroxide composite material, preparation method and applications, to solve to inhale
The actual techniques problems such as attached effect is low.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method of graphene oxide-ceric hydroxide composite material, comprising the following steps:
(1) GO and deionized water are mixed, then ultrasonic dissolution, obtains lysate；
(2) add Ce (NO into lysate made from step 13)3, it is stirred to react 0.5h at 60 DEG C, mixed liquor a is made；
(3) 20ml urea liquid is added into mixed liquor a made from step 2,2h or more is stirred at 90 DEG C, is made mixed
Close liquid b；
(4) then mixed liquor b made from step 3 is cooled to after room temperature and NaOH stirring is added, mixed liquor c is made；
(5) head product and 80 milliliters of 1M urea liquids and second obtained the centrifuge separation washing of mixed liquor c made from step 4
Alcohol mixed liquor, is then transferred to hydrothermal reaction kettle, reacts 48h at 90 DEG C, after reaction, it is cooled to room temperature and takes to reaction kettle
Out, product is made；
(6) product made from step 5 is filtered and is washed with ethyl alcohol and deionized water to neutrality, then filtrate is true
Dry in empty baking oven, then dried object moves into another oven drying, and graphene oxide-ceric hydroxide composite material is made.
Further, ultrasonic dissolution described in step 1 is that ultrasound 0.5h is realized in the case where supersonic wave cleaning machine power is 100W
's.
Further, the concentration of urea liquid described in step 3 is 2mol/L.
Further, it the condition dried in vacuum drying oven described in step 6: is dried for 24 hours at 60 DEG C.
Further, the condition of another oven drying of immigration described in step 6: the dry 12h at 85 DEG C.
The present invention also provides a kind of graphene oxide-ceric hydroxide composite materials of above-mentioned method preparation.
The present invention also provides a kind of applications of graphene oxide-ceric hydroxide composite material, are applied to Wastewater Treatment Technology
In art field, used as adsorbent.
The present invention has following effects:
(1) this experiment prepares graphene oxide-ceric hydroxide composite material by direct precipitation method and hydrothermal synthesis method
(Ce(OH)4/ GO) Congo red (CR) and phosphate anion (PO in solution are adsorbed and removed with it4 3-), and pass through SEM, FT-
IR etc. characterizes the structure of composite material, by under the conditions ofs different pH, temperature and initial mass concentration etc. to the Congo
Red (CR) and phosphate anion (PO4 3-) adsorption effect inquired into, it is determined that optimal adsorption condition be respectively as follows: pH be 7.0 Hes
6.0, adsorption time is 6 hours, and temperature is 50 DEG C and 30 DEG C.Congo red and PO is obtained by Langmuir model analysis4 3-'s
Maximal absorptive capacity is respectively 563.67mg/g, 619.63mg/g, and adsorption effect is significant, considerably beyond many suctions reported in the literature
The adsorption effect of enclosure material.
(2) present invention is combined using direct precipitation method and the hot method of hydrothermal/solvent, and it is multiple to have synthesized GO- ceric hydroxide
Condensation material is to adsorb dyestuff and phosphate radical, as a result, it has been found that significant effect, considerably beyond many similar adsorbents.The reason is that due to
π-π active force between oneself lamella is also weakened while GO is in supported rare earth, thus can be made high degree of dispersion,
The various composite materials haveing excellent performance, due to mutually forming synergistic effect between each ingredient in reaction process, improve its physics and
Chemical property.
(3) this method simple process, experimental result fidelity factor are high, the stable product of available performance.
[Detailed description of the invention]
Fig. 1 is present invention process flow diagram；
Fig. 2 is the scanning electron microscope (SEM) photograph of graphene oxide；
Fig. 3 is that the present invention implements the SEM provided figure；
Fig. 4 is the FT-IR figure of GO；
Fig. 5 is Ce (OH)4The FT-IR of/GO composite material schemes；
Fig. 6 is influence diagram of the pH value of solution to Congo red adsorbance；
Fig. 7 is influence diagram of the different initial mass concentration to Congo red adsorbance；
Fig. 8 is influence diagram of the adsorption temp to Congo red adsorbance；
Fig. 9 is pH value of solution to PO4 3-The influence diagram of adsorbance；
Figure 10 is different quality concentration to PO4 3-The influence diagram of adsorbance；
Figure 11 is adsorption temp to PO4 3-The influence diagram of adsorbance；
Figure 12 is Ce (OH)4/ GO composite material recycles figure.
■: Congo red circular regeneration is adsorbed ●: adsorb the circular regeneration of phosphate radical
[specific embodiment]
One, experimental section
1, primary raw material and instrument
The present invention implements the test material provided are as follows: graphene oxide (GO) (AA, Suzhou Tan Feng Science and Technology Ltd.), nitre
Sour cerium (Ce (NO3)3) (AR, traditional Chinese medicines chemical reagent Co., Ltd), sodium hydroxide (NaOH) (AR, the western Gansu Province chemical industry in the Guangdong Shantou City
Factory), hydrochloric acid (HCl) (AR, western Gansu Province science limited liability company), ethyl alcohol (C2H5OH) (AR, western Gansu Province science limited liability company),
Ammonium Molybdate Tetrahydrate ((NH4Mo7O24.4H2O) (AR, western Gansu Province science limited liability company), potassium dihydrogen phosphate (KH2PO4) (AR,
Western Gansu Province science limited liability company), L (+)-ascorbic acid (C6H8O6) (AR, western Gansu Province science limited liability company), it is Congo red
(C32H22N6Na2O6S2) (AR, western Gansu Province science limited liability company).
The present invention implements the instrument provided are as follows: scanning electron microscope mirror (SEM), X-ray diffraction spectra instrument (XRD), HH-
4 digital display thermostat water baths, DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus, three neck reaction flasks, 756PC type UV, visible light point
Light photometer (Shanghai Spectrum Apparatus Co., Ltd.), 1710 type Fourier transformation infrared spectrometer of PERKIN-ELMER FTIR,
The macro vacuum oven DZF-6030 of essence, spherical condensation tube, magnetic stir bar, supersonic wave cleaning machine, assay balance, bull magnetic force
Heating stirrer, air dry oven, pH meter.
2, experimental program
Ce(OH)3/ GO composite material preparation flow is shown in Fig. 1.Preparation process is as follows: being dissolved in the GO of 0.2g and has added 200mL
In the three-neck flask of deionized water and by supersonic wave cleaning machine, the ultrasound 0.5h in the case where power is 100W adds 0.8g's
Ce(NO3)3, 0.5h is stirred to react at 60 DEG C；Then the urea liquid that 20ml concentration is 2mol/L is added in mixed liquor again
It is heated with stirring to 90 DEG C or so and keeps 2h or more, make its precipitating completely, be consequently cooled to the 1MNaOH that 10ml is added in room temperature
1h is stirred, hydro-thermal will be transferred to 80 milliliters of 1M aqueous solution of urea and alcohol mixeding liquid after the head product centrifuge separation washing of synthesis
Reaction kettle (100ml, 80% filling rate stay the space 20ml), 48h is reacted at 90 DEG C, after reaction, is cooled to reaction kettle
Room temperature is taken out, and product is filtered and washed with ethyl alcohol and deionized water to neutrality, and then filtrate is in vacuum drying oven, at 60 DEG C
It is dry then to move into 85 DEG C of oven drying 12h again for 24 hours, graphene oxide-ceric hydroxide composite material (Ce is made
(OH)3/ GO composite material).
3、Ce(OH)3The measurement of/GO composite material absorption property
3.1 composite materials are to Congo red adsorption experiment
0.02g composite material adsorbent is added in the conical flask containing 100mL water, it is left to disperse 10 min by ultrasonic machine
The right side adds the liquid to be adsorbed (the Congo red stock solution of 5mmol/L) of different volumes.It is molten by the way that HCl or NaOH adjusting is added
The pH of liquid is adjusted to 7.0, overall solution volume 200mL, is placed on bull magnetic heating stirrer and magnetite is added to react 12h.After reaction,
A certain amount of mixed liquor is taken to pass through UV-vis spectrophotometer to detect concentration Congo red in water, Detection wavelength is max at this time
=498nm.It adsorbs obtained result to be fitted by Langmuir model, its suction is analyzed by obtained adsorpting data
Attached performance and its determining maximal absorptive capacity.
Congo red concentration can be analyzed by a ultraviolet visible spectrophotometer.As a result it can be calculated by formula (1)
It obtains:
Q=(C0—Ce)V/m (1)
C0、Ce: the initial concentration and equilibrium concentration (mgL) of solution
M: the volume (L) of quality (g) V: solution of adsorbent
3.2 composite materials are to PO4 3-Adsorption experiment
0.02g composite material adsorbent is added in the conical flask containing 100mL water, it is left to disperse 10 min by ultrasonic machine
The right side adds the liquid to be adsorbed (the potassium dihydrogen phosphate stock solution of 0.5mg/ml) of different volumes.It is adjusted by HCl or NaOH
The pH of solution, total volume are fixed to 200mL, are placed on bull magnetic heating stirrer and magnetite is added to react 12h.After reaction, one is taken
Quantitative mixed liquor is added 2ml ammonium molybdate and 3ml ascorbic acid, PO in water is being detected by UV-vis spectrophotometer4 3-
Concentration, Detection wavelength is max=710nm.Absorption result is fitted by Langmuir model.Pass through obtained adsorption number
According to its absorption property is analyzed, maximal absorptive capacity is determined.
PO4 3-Concentration can be calculated by above equation (1).
Below with reference to result and analysis, the invention will be further described:
Two, results and discussion
2.1, GO and Ce (OH)3The material characterization of/GO composite material
2.1.1, scanning electron microscope (SEM)
It can be observed that graphene oxide showed is lamellar structure, as silk ribbon from Fig. 2.Its lamella is very thin,
It may be seen that having the graphene oxide not of uniform size under falling off because of ultrasound, this is because the dispersibility of GO on edge
It is good, it is dispersed in water.
We can see that the Ce (OH) of soil shape from Fig. 34It is supported on above GO, there is obvious agglomeration, load
Ce(OH)4GO lamella there is fine pore, this is because Ce (OH)4/ GO composite material specific surface area becomes larger, and active site increases,
GO also weakens π-π active force between oneself lamella while supported rare earth, therefore high degree of dispersion, property can be made
The excellent composite material of energy, each ingredient forms synergistic effect between each other during the reaction, so as to overcome traditional material
The shortcomings that, improve its physical and chemical properties.
2.1.2 Fourier transformation infrared spectrometer (FT-IR)
As seen from Figure 4, the stretching vibration peak of the O-H of GO is in 3385cm-1And 1220cm-1Place, this is by sp2Carbon bone is drawn
It rises, C-O-C stretching vibration peak, C-OH stretching vibration peak and C=C stretching vibration peak are respectively 1045cm-1, 1374cm-1With
1619cm-1, in 1725cm-1Place has-COOH group on C=O stretching vibration peak, these peaks illustrate on GO containing carboxyl,
The oxygen-containing functional groups such as hydroxyl and epoxy group.
Ce (OH) as shown in Figure 54There is O-H (3449cm respectively in/GO sample-1) stretching vibration, O-H in carboxyl
(3192cm-1) in stretching vibration and carboxylate C=O antisymmetric stretching vibration in 1575cm-1Exist with symmetrical stretching vibration
1385cm-1The infrared signature absorption peak of equal functional groups, this explanation is at load C e (OH)4Afterwards, a large amount of carboxyls in the surface GO and Ce ion
In conjunction with formation chemical bond, other a variety of functional group's characteristic peaks on the surface GO obviously weaken or disappear.Therefore, it could be assumed that, oxygen
Graphite alkene and Ce (OH)4Between there is good interface compatibility, combined with chemical bond, load effect is good.
The 2.2 composite materials result Congo red to absorption
2.2.1pH the influence Congo red to absorption
Influence of the pH to adsorbent is very big, therefore selecting a suitable pH is that adsorbent obtains maximal absorptive capacity
One of premise.Selecting initial Congo red mass concentration is 16.5mg.L-1, adsorption time 6h, the item that adsorption temp is 25 DEG C
Under part, pH is to Ce (OH)3It is as shown in Figure 6 that/GO adsorbs Congo red influence: pH is obviously increased from 5-7 adsorbance, is adsorbed from 7-9
Rapid decrease, optimal absorption pH are 7, Ce (OH) to amount again4/ GO is that a variety of reactions are common to the adsorption effect of congo red
Caused by the result of effect:
1. when pH value of solution is 7, Ce (OH)3The surface /GO is positively charged, and CR is anionic dye, negatively charged, Ce
(OH)3/ GO is Electrostatic Absorption to the effect of CR；
2. as pH < 7, extra H+In conjunction with anionic dye, influence the absorption of adsorption site, therefore in low pH,
The absorption property of adsorbent is poor；
3. absorption property decline is because of OH as pH > 7OnePresence be unfavorable for the reduction of azo bond, adsorbent surface is negative
Charge gradually increases, and repels each other with again with the Congo red of negative electrical charge, and with CR anion competitive adsorption site.
Therefore, it is best that pH, which is 7 or so adsorption effects,.
2.2.2 the initial mass concentration influence Congo red to absorption
Being selected as pH in solution is 7, and adsorption time is selected as 6h, and adsorption temp is selected as under 25 DEG C of operating condition, just
Influence of the Congo red mass concentration that begins to Congo red adsorbance as shown in fig. 7, with initial Congo red mass concentration continuous increasing
Greatly, Congo red adsorbance also increases with it, and starts adsorbance and increases comparatively fast, adsorbance increase slows down when reaching a certain concentration.
It, will with Congo red effective collision probability with the continuous increase of Congo red mass concentration when absorption agent content is certain
Increase, adsorbance also will increase.After adsorbent absorption reaches saturation, the adsorption site on surface will absorbate account for completely
According to adsorbance will reach balance at this moment, no longer obviously increase.
2.2.3 the temperature influence Congo red to absorption
Under the conditions of optimal pH is 7, initial mass concentration is selected as 266.29mg.g-1, adsorption time is selected as 6h, inhales
Influence of the enclosure temperature to Congo red adsorbance is as shown in Figure 8: when adsorption temp is 30-50 DEG C, Ce (OH)3/ GO is compound
Adsorption capacities of materials is slowly increased, but when 50-60 DEG C, with increasing for temperature, adsorbance tends to balance, and adsorbance starts
It being gradually reduced, under conditions of 50 DEG C or so, adsorbance reaches maximum, and adsorption effect is best, so, the selection of optimal adsorption temperature
50℃。
2.2.4 composite material adsorbs Congo red adsorption isotherm
In this experiment, we are described with Langmuir isothermal adsorpting equation (see formula (2)) under the conditions of optimal adsorption
Composite material Ce (OH)4/ GO is to Congo red adsorption process.
ρe/qe=ρe/qm+1/bqm (2)
ρe: Congo red mass concentration, mg/L in solution when adsorption equilibrium
qe: equilibrium adsorption capacity, mg/g qm: saturated extent of adsorption, mg/g
B:Langmuir adsorption coefficient, L/mg
The fitting result of 1 isothermal adsorpting equation of table
As shown in Table 1, the R of Langmuir isothermal adsorpting equation2It is 0.9987, it can be accurately to Ce (OH)4/ GO is compound
Material adsorbs Congo red adsorption process and is described, we can obtain its saturation according to the fitting of Langmuir isothermal adsorpting equation
Adsorbance is 563.67mg/g.
2.2.5 brief summary
It can be obtained by experiment, the Optimal pH of solution absorption is selected as 7, and adsorption time selects 6h, the selection of optimal adsorption temperature
50℃.Under the adsorption conditions that adsorption temp selects 25 DEG C, with Ce (OH)3/ GO composite material is that adsorbent processing is different initial
The Congo red and corresponding adsorbance of various concentration is substituted into Langmuir isothermal adsorpting equation, intended by the Congo red solution of mass concentration
The maximum saturation adsorbance that conjunction can obtain it is 563.67mg/g.Adsorption effect is significant, substantially exceeds composite material reported in the literature
Adsorbance.
2.3 composite materials are to PO4 3-Absorption result discussion
2.3.1 composite material is to PO4 3-Adsorption experiment
0.02g composite material adsorbent is added in the conical flask containing 100mL water, it is left to disperse 10 min by ultrasonic machine
The right side adds the liquid to be adsorbed (the potassium dihydrogen phosphate stock solution of 0.5mg/ml) of different volumes.It is adjusted by HCl or NaOH
The pH of solution is adjusted to 5.6, and total volume is fixed to 200mL, is placed on bull magnetic heating stirrer and magnetite is added to react 12h.It reacted
Afterwards, a certain amount of mixed liquor is taken, 2ml ammonium molybdate and 3ml ascorbic acid is added, is detected by UV-vis spectrophotometer
PO in water4 3-Concentration, Detection wavelength is max=710nm.Absorption result is fitted by Langmuir model.By
To adsorpting data analyze its absorption property, determine maximal absorptive capacity.
PO4 3-Concentration can be calculated by above equation (1).
2.3.2 pH is to absorption PO4 3-Influence
Influence of the pH to adsorbent is huge, therefore selecting a suitable pH is the premise that adsorbent obtains maximal absorptive capacity
One of.In selection initial p O4 3-Mass concentration is 53.52mg.L-1, adsorption time is selected as 6h, and adsorption temp is selected as 25 DEG C
Under the conditions of, pH is to Ce (OH)4The influence of/GO is as shown in Figure 9: in 5-6, adsorbance gradually increases pH, pH=6-9 adsorbance
Rapid decrease show that the Optimal pH of absorption is 6.0, and maximal absorptive capacity is 513mg.g at this time-1.This is because Ce (OH)4/ GO inhales
Attached PO4 3-It is caused by a variety of coefficient results of reaction: since rare earth metal is positively charged, to negatively charged PO4 3--
Have biggish adsorptivity and GO large specific surface area, there is a more active site, but due to pH in 5-6 La (OH)3/ GO contains
Oxygen functional group protonation is reinforced, itself and PO are made4 3-Between Interaction enhanced, therefore possess very strong adsorption capacity, institute
With selecting solution optimal adsorption pH is 6.0 or so.
2.3.3 concentration is to absorption PO4 3-Influence
It is 6.0 in pH value of solution, adsorption time selects 6h, and adsorption temp is selected as under conditions of 25 DEG C, initial p O4 3-Quality
Concentration is to PO4 3-The influence of adsorbance is as shown in Figure 10, with initial p O4 3-The continuous increase of mass concentration, PO4 3-Adsorbance
Also it can increase with it, when absorption agent content is certain, with PO4 3-The continuous increase of mass concentration, with PO4 3-Effective collision
Probability increases, and adsorbance just will increase.After adsorbance reaches saturation, the adsorption site of adsorbent surface will absorbate it is complete
It occupies entirely, therefore adsorbance can reach balance, gradually tend towards stability after the stock solution volume of phosphate radical reaches 30mL, at this time
Maximal absorptive capacity is close to 600mg.g-1。
2.3.4 temperature is to absorption PO4 3-Influence
6.0 are selected as in the Optimal pH of solution, initial mass concentration is selected as 49.3mg.L-1, adsorption time is selected as 6h
Adsorption conditions under, carry out the experiment of various temperature, adsorption temp is to PO4 3-The influence of adsorbance is as shown in figure 11, Ce (OH)4/
With the continuous raising of the adsorption temp of experiment, adsorbance is being gradually reduced, finally tending towards stability GO adsorbent.Pass through curve graph
Obtain: adsorption temp selects 30 DEG C as optimal adsorption temperature, and adsorption effect reaches best.
2.3.5 composite material adsorbs PO4 3-Adsorption isotherm
In this experiment, under the conditions of we describe optimal adsorption using Langmuir isothermal adsorpting equation (see formula (2))
Ce(OH)4/ GO composite material is to PO4 3-Adsorption process.
The fitting result of 2 isothermal adsorpting equation of table
As shown in Table 2, the R of Langmuir isothermal adsorpting equation2=0.9895, it can be to La (OH)3/ GO composite material is inhaled
Attached PO4 3-Adsorption process accurately described, the saturated extent of adsorption that Langmuir isothermal adsorpting equation is fitted is
619.63mg/g。
2.3.6 brief summary
It is drawn a conclusion by above-mentioned experiment, solution optimal adsorption pH is selected as 6.0, and adsorption time is selected as 6h, best to inhale
Enclosure temperature is 30 DEG C.Ce(OH)4/ GO composite material is the PO that adsorbent handles that different initial mass concentration are4 3-Solution, 25 DEG C,
By various concentration PO4 3-And corresponding adsorbance substitutes into Langmuir isothermal adsorpting equation, fitting can obtain its maximum saturation adsorbance
For 619.63mg/g, the rate of recovery still keeps 80% or more after circulation absorption 6 times.Adsorption effect is significant, substantially exceeds document report
The adsorbance of the composite material in road.
2.4 composite materials adsorb Congo red and phosphate radical solution circular regeneration
Adsorbent not only needs it efficiently quick, essentially consists in energy as the leading role for handling water pollution in daily life
Enough circular regenerations, Ce (OH)4/ GO composite material is impregnated 2 days by ethyl alcohol after for the first time to Congo red absorption, uses deionization
Water cleaning is recycled after putting air dry oven drying several times；Composite material is for the first time to PO4 3-After the absorption of solution, pass through NaOH
Solution impregnates 2 days, is cleaned after putting air dry oven drying several times and is recycled with deionized water.By Figure 12 we it is found that following
After ring uses 6 times, the adsorbent adsorption rate of recycling is declined, but still has 80% or more, so Ce (OH)4/ GO adsorbent can
It is used with repetitive cycling.
Three, conclusion
Ce (OH) is prepared by direct precipitation method and hydrothermal synthesis in this experiment4/ GO composite material uses a kind of fast
Fast efficient, simple process, adsorbent without secondary pollution is to Congo red and PO4 3-Carry out absorption research, by pH, temperature with
And it is 7 and 6.0 that initial mass concentration is probed into obtain optimal adsorption conditions to be respectively as follows: pH to pollutant, adsorption time 6
Hour, temperature is 50 DEG C and 30 DEG C.Congo red and PO is obtained by Langmuir model analysis4 3-Maximal absorptive capacity be respectively
563.67mg/g, 619.63mg/g, adsorption effect is significant and adsorbent is reusable, far more than adsorbent material reported in the literature
Adsorbance (being shown in Table 2 and 4), be expected to become water pollution treatment process in remove dyestuff and phosphorus pollution efficient, green absorption
Agent.
Saturated extent of adsorption of the different adsorbents of table 3 to Congo red (CR)
Saturated extent of adsorption of the different adsorbents of table 4 to phosphate radical
Bibliography:
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[D] South China Science & Engineering University, 2016.
[3] Li Zemu, Peng Xiaochun, Wang Qinghua, Cai Hong, Li Youji coat Co nanometers by core dendrimer of graphene
Composite material preparation and its absorption property [J] fine chemistry industry, 2016,33 (02): 200-206.
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[5] preparation of Li Lei's functional magnetic graphene adsorbent material of heap of stone and performance study [D] University Of Ji'nan, 2015.
[6] Yao Y, Miao S, Liu S, et a1.Synthesis, characterization, and adsorption
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[7] synthesis and its absorption of Wu Yan graphite woman's nanocomposite and Photocatalytic Performance Study [D] [doctorate
Paper] Guangzhou: South China Science & Engineering University, 2016
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[J] application chemical industry, 2008,37 (1): 54-66
[9] synthesis of Wu Jiao magnetism high efficiency rare-earth dephosphorization agent and adsorption mechanism research [D] [Ph.D. Dissertation] long
Spring: Northeast Normal University, 2014.
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Text] Guangzhou: Ji'nan University, 2015
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the present invention by
The scope of patent protection that the claims submitted determine.
Claims (7)
1. a kind of graphene oxide-ceric hydroxide composite material preparation method, which comprises the following steps:
(1) GO and deionized water are mixed, then ultrasonic dissolution, obtains lysate；
(2) add Ce (NO into lysate made from step 13)3, it is stirred to react 0.5h at 60 DEG C, mixed liquor a is made；
(3) 20ml urea liquid is added into mixed liquor a made from step 2,2h or more is stirred at 90 DEG C, mixed liquor b is made；
(4) then mixed liquor b made from step 3 is cooled to after room temperature and NaOH stirring is added, mixed liquor c is made；
(5) head product that the centrifuge separation washing of mixed liquor c made from step 4 obtains is mixed with 80 milliliters of 1M urea liquids and ethyl alcohol
It closes liquid and is transferred to hydrothermal reaction kettle, 48h is reacted at 90 DEG C, after reaction, is cooled to room temperature taking-up to reaction kettle, be made and produce
Object；
(6) product made from step 5 is filtered and is washed with ethyl alcohol and deionized water to neutrality, then filtrate is dried in vacuum
Dry in case, then dried object moves into another oven drying, and graphene oxide-ceric hydroxide composite material is made.
2. graphene oxide-ceric hydroxide composite material preparation method according to claim 1, it is characterised in that: step
Ultrasonic dissolution described in rapid 1 is that ultrasound 0.5h is realized in the case where supersonic wave cleaning machine power is 100W.
3. graphene oxide-ceric hydroxide composite material preparation method according to claim 1, it is characterised in that: step
The concentration of urea liquid described in rapid 3 is 2mol/L.
4. graphene oxide-ceric hydroxide composite material preparation method according to claim 1, it is characterised in that: step
The condition dried in vacuum drying oven described in rapid 6: it is dried for 24 hours at 60 DEG C.
5. graphene oxide-ceric hydroxide composite material preparation method according to claim 1, it is characterised in that: step
The condition of another oven drying of immigration described in rapid 6: the dry 12h at 85 DEG C.
6. a kind of graphene oxide-ceric hydroxide composite material of method preparation according to claim 1-5.
7. a kind of application of graphene oxide according to claim 6-ceric hydroxide composite material, it is characterised in that:
Applied in technical field of waste water processing, used as adsorbent.
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