Background technology
Due to warming for global climate, energy resource structure needs to reform and optimize, and is selected as the carbon-free replacement of fossil fuel
Item is selected, nuclear energy is widely used by various countries.As a kind of important energy source, nuclear energy already takes up 5.7% and the world of world energy sources
The 13% of electric power.But the operation of nuclear power station will produce a large amount of waste materials with high radioactivity, and a large amount of radioactivity is same in these waste materials
Position element, as caused by because of earthquake or mistake accident due to can be discharged into environment, ecocatastrophe can be caused.It is same in these radioactivity
In the element of position, Ce 137 is the major radiation component in waste material, long half time(30.4), the gamma-radiation for the generation that decays is strong, sternly
The health of the mankind is threatened again.In addition, solubility is high in water for cesium salt, biosphere can be migrated into rapidly by underground water.This
Outside, the property of caesium is identical as potassium and sodium, is easy to be absorbed by terrestrial and aquatile, is enriched in body by food chain
On tissue and organ.Moreover, Ce 137 can be propagated dust through the air, and then contaminated food products and drinking water.It is chronically exposed to
Under the Ce 137 of high dose, one of the worst situation is to suffer from thyroid cancer.Accordingly, it is considered to the danger of nuclear pollution, radioactivity
Caesium should be removed away from nuke rubbish by efficient selective.
In recent years, many strategies are for removing the Ce 137 in nuke rubbish waste water, for example evaporation, solvent extraction, reunite and sink
Shallow lake, ion exchange, microfiltration and film engineering etc..Due to ion-exchange eliminate Ce 137 method it is easy, it is efficient and selection
Property is good, thus shows one's talent in these techniques.Inorganic ion exchanger, such as zeolite sodium titanate, silicon metatitanic acid and heteropoly acid, by
In its higher thermal stability and compatible with final nuclear waste type body, have been used in the processing of nuclear waste water.However, utilizing
Ion exchange technique removal Ce 137 at this stage will will produce a large amount of secondary nuke rubbish.It, will in order to reduce secondary nuke rubbish to the greatest extent
Ion exchange technique is combined with electrochemical method and isolates Ce 137 for selectivity is reversible from nuke rubbish waste water.
In this electro-chemical conversion ion exchange process, the enrichment or separation of ion can be anti-by regulating and controlling redox on electrode interface
It should control, to maintain electroneutral.
More than ten years in past, the transition metal iron cyanide have been widely used for going for radioactive cesium as ion-exchanger
It removes.The cube network structure of its zeolite shape can provide larger gap to accommodate alkali metal ion.Not all hydration alkali
Metal ion can be spread in the hole of these metal iron cyanide skeletons.Such as lithium ion and sodium ion, due to its be hydrated from
Sub-volume is big and hardly enters in metal iron cyanide lattice.Therefore, the metal iron cyanide shows the separation and removal of Ce 137
Higher selectivity.In addition, the iron at these metal organic structure centers has very high electrochemical invertibity, redox reaction
Process is along with ion exchange to maintain electroneutral.
However, the simple metal iron cyanide is as electrochemically converting, ion exchange is inefficient in the removal of Ce 137, this is
Because its electric conductivity is low, stability is poor and surface area is not high.A kind of feasible solution is in metal iron cyanide electrochemistry
Carbon carrier is introduced in conversion ions exchanger, these carbon carriers potentially act as nano-electrode to transmit electronics.It is carried in addition, introducing carbon
The advantages of body, is that it can improve the dispersibility of metal iron cyanide nano-particle, avoids metal iron cyanide nano-particle from electricity
Pole surface is detached from.
In carbon material, as a kind of carbon carrier of only monatomic thickness, graphene price is low, good conductivity and specific surface
Product is big, causes the great interest of people.Under polyvinylpyrrolidone existence condition, it can be prepared by coprecipitation method in situ
Iron nickel cyanide/redox graphene hybrid material.Experiment display, iron cyaniding nickel nano particle are dispersed in oxygen reduction fossil
On black alkene, particle size 60nm.Prepared nickel cyanide/redox graphene hybrid material can be used for Ce 137
Separation.Compared with pure iron nickel cyanide, iron nickel cyanide/redox graphene hybrid material in terms of the removal of caesium selectivity and
It is more efficient.In addition, in cesium ion solution, the electro-chemical conversion ion of iron nickel cyanide/redox graphene hybrid material
Exchange stability higher.Just due to its outstanding cesium ion removal capacity, iron nickel cyanide/redox graphene hybrid material is made
It is expected to be applied in technical grade nuke rubbish liquid waste processing for a kind of advanced electro-chemical conversion ion-exchanger.This patent Shen
Please by Zhejiang Province's non-profit foundation project(No.2016C33011)With Zhejiang Province's nature fund project(No.Y17B030005)Branch
It holds.
Invention content
The present invention is to overcome above-mentioned technical problem and improve its profit when large-scale use electrochemically converts ion-exchanger
A kind of preparation method of iron nickel cyanide/redox graphene hybrid material is provided with efficiency, this method passes through simple
Coprecipitation method prepares the iron cyaniding nickel nano particle of redox graphene support, and wherein iron cyaniding nickel nano particle uniformly divides
It is dispersed on redox graphene, average grain diameter 60nm.Iron nickel cyanide/redox graphene hydridization made from this method
It is shown under the conditions of material is existing for potassium ion to the higher selectivity of cesium ion, therefore can be used as highly selective electrochemistry
Remove the electro-chemical conversion ion-exchanger of cesium ion.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of iron nickel cyanide/redox graphene
The preparation method of hybrid material, it is characterised in that the specific steps are:
(1)The preparation of graphene oxide surpasses after mixing 0.1-0.9g graphite powders with 15mL salpeter solutions and 30mL sulfuric acid solutions
0.1-6g potassium permanganate is added portionwise in mixed liquor and is stirred 1-10h by sound ice bath 10-120min in 20-100 DEG C, then will
Mixed liquor is diluted to 250mL with deionized water, and excessive potassium permanganate is the double of 10%-30% by the way that 5-50mL mass concentrations are added
The reaction removal of oxygen water, graphene oxide are obtained by centrifuging, then the hydrochloric acid solution of 1mol/L and ethyl alcohol is used to rinse respectively, so
Dialysis is carried out in deionized water afterwards until the pH value of graphene oxide solution is neutrality;
(2)5-50mg polyvinylpyrrolidones are dissolved in 5-30mL graphene oxide solutions simultaneously by the preparation of redox graphene
It is diluted to 50mL with deionized water, stirs and the hydrazine hydrate that 1mL mass concentrations are 10%-100% is added to mixed liquor after 30min
In, in 20-100 DEG C under agitation reduction reaction cleaned gone back with deionized water and ethyl alcohol successively for 24 hours, after centrifugation
Former graphene oxide;
(3)The preparation of iron nickel cyanide/redox graphene hybrid material, by 0.1-10mmol NiCl2With 1-20mg oxygen reductions
Graphite alkene mixes in 100mL deionized waters, then by 0.1-5mmol K3[Fe(CN)6] be added portionwise in mixed liquor with shape
At precipitation, 6h is then stirred by ultrasonic, is cleaned to obtain iron nickel cyanide/reduction-oxidation with deionized water and ethyl alcohol successively after centrifugation
Graphene hybrid material.
Iron nickel cyanide of the present invention/redox graphene hybrid material exists as ion-exchanger is electrochemically converted
Application in the processing of technical grade nuke rubbish waste liquid cesium ion.
Iron nickel cyanide of the present invention/redox graphene hybrid material exists as ion-exchanger is electrochemically converted
Application in highly selective electrochemistry removal cesium ion, to the maximum adsorption capacity of cesium ion in 1mol/L Klorvess Liquids
For 292mg g-1, breadth coefficient reaches 594L.g-1。
Iron nickel cyanide of the present invention/redox graphene hybrid material exists as ion-exchanger is electrochemically converted
Application in the processing of technical grade nuke rubbish waste liquid cesium ion, it is characterised in that detailed process is:Adsorption process be by iron nickel cyanide/
Redox graphene hybrid material electrode be placed in technical grade nuke rubbish waste liquid 0.3-0.5V constant potential polarizations 10-400s with
Realize the highly selective removal of cesium ion, desorption process is in 0.8-1.2V constant potential polarizations 10-400s to realize cesium ion
It is desorbed, the iron nickel cyanide after desorption/redox graphene hybrid material electrode repetitive cycling uses.
The present invention has the advantages that compared with prior art:The present invention prepares iron cyanogen by coprecipitation method in situ
Change nickel/redox graphene hybrid material, iron cyaniding nickel nano particle uniform load is on redox graphene, grain size
Size is 60nm, and the iron nickel cyanide/redox graphene hybrid material is as a kind of novel electro-chemical conversion ion exchange
Agent is 292mg g to the maximum adsorption capacity of cesium ion in 1mol/L Klorvess Liquids-1, breadth coefficient reaches 594L.g-1, it is far above the maximum adsorption capacity 220mg g of pure iron nickel cyanide-1With breadth coefficient 350L g-1.Iron nickel cyanide/reduction-oxidation
Graphene hybrid material is than the cyclical stability higher of pure iron nickel cyanide, therefore iron nickel cyanide/redox graphene hybrid material
It is expected to as a kind of effective processing for electrochemically converting ion-exchanger for nuclear industry waste material waste liquid cesium ion.
Embodiment
The preparation of graphene oxide
Ultrasonic ice bath 30min after 0.5g graphite powders are mixed with 15mL salpeter solutions and 30mL sulfuric acid solutions, in 30 DEG C by 3g high
Potassium manganate is added portionwise in mixed liquor and stirs 5h, and mixed liquor is then diluted to 250mL, excessive permanganic acid with deionized water
Potassium reacts removal by the way that the hydrogen peroxide that 10mL mass concentrations are 30% is added, and graphene oxide is obtained by centrifuging, then is distinguished
It is rinsed with the hydrochloric acid solution and ethyl alcohol of 1mol/L, then carries out the pH value dialysed up to graphene oxide solution in deionized water
For neutrality;
The preparation of redox graphene
20mg polyvinylpyrrolidones are dissolved in 10mL graphene oxide solutions and are diluted to 50mL with deionized water, are stirred
The hydrazine hydrate that 1mL mass concentrations are 90% is added in mixed liquor after 30min, in 100 DEG C of reduction reactions under agitation
For 24 hours, it cleans to obtain redox graphene with deionized water and ethyl alcohol successively after centrifugation;
The preparation of iron nickel cyanide/redox graphene hybrid material
By 3mmol NiCl2It is mixed in 100mL deionized waters with 10mg redox graphenes, then by 2mmol K3[Fe
(CN)6] be added portionwise in mixed liquor with formed precipitation, 6h is then stirred by ultrasonic, after centrifugation successively use deionized water and
Ethyl alcohol cleans to obtain iron nickel cyanide/redox graphene hybrid material.As a comparison, pure iron nickel cyanide same procedure system
It is standby.
Characterization
Iron nickel cyanide/redox graphene hybrid material is observed with JEOL-2010 transmission electron microscopes, and accelerating potential is
200kV, distribution diagram of element are composed by X-ray energy dispersion to characterize, and high angle ring-type details in a play not acted out on stage, but told through dialogues scanning transmission electron microscope mould is taken
Formula, accelerating potential 300kV.
The composition of iron nickel cyanide/redox graphene hybrid material can pass through x-ray photoelectron spectroscopy
(ESCALAB-MKII)With Plasma-Atomic Emission spectrum(TJA Atomscan Advantage instrument)Carry out table
Sign, crystal structure are analyzed by X-ray powder diffraction spectrum(Philips X’PertMPD).
Electrochemical Properties
Cyclic voltammetry(CV)With timing Amperometric(CA)It is to be carried out in typical three electrode cell, which is connected to
In CHI660C electrochemical workstations.4mg iron nickel cyanide/redox graphene hybrid material drop coating is on glass-carbon electrode(Diameter
2cm)And as working electrode.Saturated calomel electrode is reference electrode, and gauze platinum electrode is to electrode.Electrochemical alternate impedance spectrum
Measurement frequency ranging from 100kHz to 0.1Hz, current potential are the Middle Eocene of the relevant redox reaction of alkali metal ion.
Electrochemical adsorption is to be realized under magnetic stirring by timing Amperometric, and monitored by energy dispersion spectrum.
Each energy dispersion spectrogram is obtained in the section of 1*1mm scanning 15min.
Cesium ion removal capacity uses adsorption capacity QeTo characterize:
Wherein, mCsFor the quality that cesium ion adsorbs in adsorbent, M is the quality of adsorbent itself, and cesium ion is in adsorbent
Quality can be obtained by energy dispersion spectrum.
The selectivity of cesium ion is characterized with breadth coefficient:
Wherein, CeConcentration when reaching balance in the solution for cesium ion in solution can be examined by Plasma-Atomic absorption
It surveys.
Material characterization
The pattern of iron nickel cyanide/redox graphene hybrid material can be characterized by transmission electron microscope.Figure 1A shows iron cyanogen
Change nickel nano particle to be dispersed on redox graphene, particle size statistics is 60nm(Figure 1B), high-resolution transmission
Electronic Speculum shows that iron cyaniding nickel nano particle is amorphous(Fig. 1 C), the iron cyaniding nickel nano particle element on redox graphene
Distribution is composed with energy dispersion and is obtained under angle of elevation annular dark field pattern by scanning transmission electron microscope technology(Fig. 1 D-G).It is clear in figure
Show that N, Fe and Ni element are evenly distributed on single iron cyaniding nickel nano particle, energy dispersion spectrum Surface scan figure provides also
The N of iron cyaniding nickel nano particle on former graphene oxide:Cu:The atomic ratio of Fe is 6:1.25:1, with K0.5Ni2.5[Fe(CN)6]2
The metering of element constitutional chemistry than consistent.And pure iron nickel cyanide is displayed without specific pattern, and particle size distribution range is wider.
The crystal structure of pure iron nickel cyanide and iron nickel cyanide/redox graphene hybrid material passes through powder diffraction techniques
It is characterized.If Fig. 2 is shown, all diffraction maximums of pure iron nickel cyanide can correspond to a cube KNiFe (CN)6(JCPDS
no.51-1897).The powder diagram of iron nickel cyanide/redox graphene hybrid material is similar to pure iron nickel cyanide, only
It is to be 15 ° in the angle of diffraction an inapparent broad peak occur to 30o, comes from graphene(002)Face.Pure iron nickel cyanide
It can be shown by the x-ray photoelectron spectroscopy of the sample with the composition of iron nickel cyanide/redox graphene hybrid material
(Fig. 2 B), it is 1.2 in conjunction with the atomic ratio that energy peak about corresponds respectively to nickel 2p and iron 2p, Ni and Fe in 717eV and 868eV:
1, it is consistent with the result of energy dispersion spectrum(Fig. 2 C).The chemistry of carbon on iron nickel cyanide/redox graphene hybrid material
Valence state is studied by the energy spectrum signal of high-resolution C1s.Shown in Fig. 2 D, the matched curve figure of redox graphene C1s is aobvious
Show the peak of the oxide there are three carbon, alcohol oxygroup(286.0eV), carbonyl(288.0eV)And carboxyl(289.0eV).They are accounted for altogether
6.8% carbon on redox graphene illustrates that graphene oxide is successfully converted to redox graphene.For iron cyanogen
Change nickel/redox graphene hybrid material, C-N components also appear in 286.0eV, and with the signal overlap of alcohol oxygroup, say
Bright iron nickel cyanide is supported on redox graphene.
Electrochemically convert ion exchange mechanism
The electro-chemical conversion ion exchange mechanism of pure iron nickel cyanide be 0.1M alkali metal ions solution by cyclic voltammetry come
Research(Fig. 3 A).Other than cesium ion, all cyclic voltammograms, which are all shown, has higher electrochemistry can alkali metal ion
Inverse property.It is the absorption and release of alkali metal ion along with redox reaction to pure iron nickel cyanide:
A=Li, Na, K or Rb.
Pure iron nickel cyanide is a Quasi-reversible process to the electrochemical reaction of cesium ion unlike other metal ions
(Fig. 3 B).In addition, in cesium ion solution, pure iron nickel cyanide is shown compared with partial circulating volt-ampere ring, illustrates cesium ion in iron nickel cyanide
Lattice intermediate ion exchange capacity it is smaller.In addition, redox reaction of the iron nickel cyanide to the electrochemical response of alkali metal ion
Middle Eocene in the following order be incremented by:Li+(0.275V)、Na+(0.365V)、K+(0.447V)、Rb+(0.596V)And Cs+
(0.657V), consistent with the size order of the radius of ion(Li+0.60, Na+0.95, K+1.33 Rb+ 1.48
, Cs+1.69Å).
Iron nickel cyanide/redox graphene hybrid material is similar to pure iron cyanogen to the electrochemical reaction of alkali metal ion
Change nickel, the difference is that, since alkali metal ion electrochemically converts on iron nickel cyanide/redox graphene hybrid material
The peak difference smaller of the cyclic voltammogram of ion exchange, peak current are more symmetrical.Thus alkali metal ion is in iron nickel cyanide/reduction-oxidation
The electrochemical response of graphene hybrid material is more reversible.In addition, the exchange of iron nickel cyanide/redox graphene hybrid material
Capacity is larger, this can be confirmed from larger cyclic voltammetric ring.Iron nickel cyanide/redox graphene hybrid material is excellent
It is related with redox graphene to electrochemically convert ion-exchange performance.The introducing of redox graphene is beneficial to electronics biography
It passs, accelerates alkali metal ion in the insertion of iron nickel cyanide lattice.
The electro-chemical conversion that AC impedance electrochemical technology is also used for iron nickel cyanide/redox graphene hybrid material is handed over
Flow the Middle Eocene of the ion exchange of iron nickel cyanide/redox graphene hybrid material shown in volt-ampere mechanism study Fig. 3 C
Nyquist schemes.Nonlinear least square fitting technology can be utilized to be used for simulating equivalent circuit figure(Illustration in Fig. 3), all
Nyquist figures include three sections.In low frequency section, Nyquist figures are shown as almost vertical straight line, this is derived from normal phase angle member
Part, it is related to materials double-layer capacitance, indicate that iron nickel cyanide/redox graphene hybrid material surface area is larger.In low frequency range
Between, Nyquist figures are a semi arches, this is related with interface charge transmission resistance.And intermediate frequency area, Nyquist figures are one
A straight line for carrying 45 ° of inclination angles.The impedance of this transition interval frequency is defined as Warburg impedance Z w, it exists with electrolyte
The upper ion diffusion of electrode interface is related.In alkali metal ion, it is maximum that cesium ion interface charge transmits resistance(80Ω), say
It is bright existing for cesium ion under the conditions of, iron nickel cyanide electron transmission is a slow process.In addition, the Warburg resistances of cesium ion
Anti- Zw is also maximum(15Ω), it is difficult to illustrate that the cesium ion of larger ionic radius can cause to spread in iron nickel cyanide.
Cesium ion removal capacity
Selective removal cesium ion has practical significance in the processing of nuke rubbish in the alkali metal ion coexisted from other.Fig. 4 A
Show pure iron nickel cyanide the 0.05M Klorvess Liquids containing different cesium ion concentrations cyclic voltammogram, due to cesium ion
The response current of response current and potassium ion is superimposed, it is difficult to by the response signal of caesium from the relevant cyclic voltammetric of potassium ion
It is separated in curve.The increase of cesium ion concentration can inhibit the response current of potassium ion, at the same can make potassium ion absorption it is excessively electric
Position increases, and illustrates that the selectivity that iron nickel cyanide responds potassium ion the response ratio of cesium ion wants high.To iron nickel cyanide/reduction
Graphene oxide hybrid material, when cesium ion concentration increases in 0.5M Klorvess Liquids, cyclic voltammogram is also shown as together
The trend of sample(Fig. 4 B).Unlike, for iron nickel cyanide/redox graphene hybrid material, go out in cyclic voltammogram
Show outside the relevant redox peaks of potassium ion, in the electrode potential section of corrigendum, the relevant redox of cesium ion has occurred
Peak, and with the increase of cesium ion concentration, which moves to positive potential.In addition, its peak current starts to increase, in high concentration
In cesium ion solution(≥0.01M)Tend to stablize.Fig. 4 C show pair of potassium ion relevant oxidation peak current and cesium ion concentration
Number relationship.For pure iron nickel cyanide and iron nickel cyanide/redox graphene hybrid material, in low concentration cesium ion solution
In, the response current of potassium ion and the logarithm of cesium ion concentration are at negative linear relationship.For pure iron nickel cyanide, iron cyanogen
The slope for changing the calibration curve of nickel/redox graphene hybrid material is larger, and the range of linearity is wider, illustrates and pure iron nickel cyanide
It compares, iron nickel cyanide/redox graphene hybrid material responds cesium ion sensitiveer.Iron nickel cyanide responds cesium ion
Selectivity is main reason is that cesium ion can accommodate cesium ion than the ionic radius bigger and iron nickel cyanide lattice of potassium ion
Space is limited.After cesium ion is adsorbed into inside iron nickel cyanide lattice, the cesium ion for being limited to iron nickel cyanide lattice is difficult to expand
It sheds.Therefore, the current-responsive of potassium ion will be suppressed, and response pctential will be to shuffling.
Iron nickel cyanide/redox graphene hybrid material can pass through timing Amperometric to the absorption and release of cesium ion
To realize.Stable state electricity of the iron nickel cyanide/redox graphene hybrid material as shown in Figure 5A in 1mM cesium chloride solutions 0.8V
Stream is oxidation current, and is reduction current in the steady-state current of 0.5 V.The constituent content and valence state of iron nickel cyanide in hybrid material
Variation can be studied with x-ray photoelectron spectroscopy.The iron nickel cyanide of reduction-state is higher than oxidation state to the load capacity of cesium ion
Iron nickel cyanide(Fig. 5 B), right under the conditions of in order to study iron nickel cyanide/redox graphene hybrid material existing for potassium ion
The selectivity that cesium ion absorbs, we have studied reduction-state iron nickel cyanide/redox graphene hybrid material and iron nickel cyanides
Contain different content cesium ion in 1M potassium chloride and reach after adsorption equilibrium the spectrum of the X-ray energy dispersion after background correction.To iron
Nickel cyanide/redox graphene hybrid material, cesium ion and potassium ion is all that can measure in the content of all solution(Figure
6A).And for iron nickel cyanide, until cesium ion concentration reaches 1 × 10 in solution-4M just will appear the peak of apparent caesium(Fig. 6 B).Separately
On the one hand, the cesium ion in Klorvess Liquid can inhibit the X-ray energy dispersion spectrum signal of potassium ion.Illustrate that iron nickel cyanide is brilliant
Cesium ion in lattice can repel the insertion of potassium ion, this is consistent with cyclic voltammetric data.Fig. 6 C show that cesium ion and potassium ion are inhaled
Attached capacity and the relationship between cesium ion concentration in solution.In 1M Klorvess Liquids, iron nickel cyanide/redox graphene is miscellaneous
Change material and 292mg g are reached to the adsorption capacity of cesium ion-1, higher than iron nickel cyanide to the adsorption capacity of cesium ion(220mg∙g-1).With the increase of cesium ion concentration in solution, iron nickel cyanide/redox graphene hybrid material holds the absorption of potassium ion
It measures from 251mg g-1Reduce to 35mg g-1, and pure iron nickel cyanide to the adsorption capacity of potassium ion from 140mg g-1Reduce to 33mg g-1。
The relationship of cesium ion concentration in the breadth coefficient and solution of Fig. 6 D display cesium ions.Contain 5 × 10 in 1M Klorvess Liquids-4M
Cesium ion, iron nickel cyanide/redox graphene hybrid material reach maximum value to the breadth coefficient of cesium ion, are 594L g-1,
Higher than the 350L g of the breadth coefficient of pure iron nickel cyanide-1.And under the conditions of no potassium ion, iron nickel cyanide/reduction-oxidation graphite
Alkene hybrid material is 5 × 10-4In M cesium ion solution, breadth coefficient reaches 610L g-1, the value and hybrid material 1M potassium from
Breadth coefficient peak value is close in sub- solution.In addition, the breadth coefficient value obtained using Electrochemical adsorption method is than conventional chemical
The breadth coefficient value that adsorption method obtains is big.For iron nickel cyanide/redox graphene hybrid material, by electrochemistry side
The breadth coefficient and maximum adsorption capacity that method obtains are quite or better than recent other metallic iron nickel cyanide adsorbents(Table 1).
The maximal absorptive capacity of 1 iron nickel cyanide of table/redox graphene hybrid material(Qmax)And breadth coefficient(Kd)
Durability is tested
For electrochemically converting ion-exchanger, service life is extremely important to handling nuclear pollution on a large scale.It the absorption of caesium and releases
Put is controlled using timing Amperometric in 1mM cesium chloride solutions.The adsorption potential control of cesium ion exists in 0.5V, desorption current potential
0.8V, absorption or desorption time are 200s every time, this process repeats 160 times.Shown in Fig. 7, for iron nickel cyanide/reduction-oxidation
Graphene hybrid material, in primary absorption and de-adsorption cycle, anode current is almost equal with cathode current, illustrates cesium ion energy
It is enough to diffuse into quickly in the lattice of iron nickel cyanide, and reach equilibrium state in the desorption of cesium ion and absorption.On the contrary, for pure
Iron nickel cyanide, anode current and cathode current are uneven, illustrate that cesium ion in the diffusion of iron nickel cyanide is irreversible.Its oxygen
Change reduction current after starting to recycle several times to decay rapidly, this may be since falling off for iron nickel cyanide is related.
In conclusion the present invention, which has developed a kind of feasible coprecipitation method in situ, prepares iron nickel cyanide/oxygen reduction fossil
Black alkene hybrid material, iron cyaniding nickel nano particle are uniformly supported on redox graphene, particle size 60nm.Make
For a kind of model electrochemical conversion ions exchanger, in 1M Klorvess Liquids, maximum adsorption capacity is 292mg g-1, distribution
Coefficient can reach 594L.g-1, it is far above the maximum adsorption capacity 220mg g of pure iron nickel cyanide-1With breadth coefficient 350L g-1.With
Pure iron nickel cyanide is compared, iron nickel cyanide/redox graphene hybrid material than pure iron nickel cyanide cyclical stability higher, this
The removal capacity of the excellent cesium ion of kind is attributed to the graphene of hybrid material, it can shift electronics, accelerate cesium ion in iron
It is spread in nickel cyanide lattice.Therefore, iron nickel cyanide/redox graphene hybrid material is expected to as a kind of effective cost-effective
Ion-exchanger is electrochemically converted for the processing of nuclear industry waste material cesium ion.
Embodiment above describes the basic principles and main features and advantage of the present invention, and the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the originals of the present invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.