CN104324690B - Magnetic bimodal mesoporous carbon of iron content nickel bimetal and its preparation method and application - Google Patents

Magnetic bimodal mesoporous carbon of iron content nickel bimetal and its preparation method and application Download PDF

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CN104324690B
CN104324690B CN201410604753.3A CN201410604753A CN104324690B CN 104324690 B CN104324690 B CN 104324690B CN 201410604753 A CN201410604753 A CN 201410604753A CN 104324690 B CN104324690 B CN 104324690B
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magnetic
mesoporous carbon
iron content
content nickel
nickel bimetal
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CN104324690A (en
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刘媛媛
曾光明
汤琳
杨贵德
章毅
庞娅
蔡叶
周耀渝
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Hunan University
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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
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28088—Pore-size distribution
    • B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents

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Abstract

Magnetic bimodal mesoporous carbon that the invention discloses a kind of iron content nickel bimetal and its preparation method and application, the magnetic bimodal mesoporous carbon of this iron content nickel bimetal is with magnetic bimodal mesoporous carbon as carrier, and iron-nickel alloy nano-particle is dispersed in magnetic bimodal mesoporous carbon formation aperture and is respectively the orderly bimodal mesoporous structure of 4nm～5nm and 15nm～20nm.Its preparation method includes preparing mesoporous silicon template, prepares the step such as magnetic bimodal mesoporous carbon of complex, preparation iron content nickel bimetal.The present invention uses incipient wetness impregnation method to prepare the magnetic bimodal mesoporous carbon of iron content nickel bimetal, the magnetic bimodal mesoporous carbon ratio surface area of the iron content nickel bimetal prepared is big, iron-nickel alloy nano-particle is evenly distributed, it is difficult to reunite, magnetic performance is excellent, and stable in physicochemical property, can be applicable to the removal of dyes pollutant, have that adsorption capacity is big, removal efficiency is high, wide accommodation, an advantage such as easy and simple to handle, practical.

Description

Magnetic bimodal mesoporous carbon of iron content nickel bimetal and its preparation method and application
Technical field
The present invention relates to field of waste water treatment, be specifically related to magnetic bimodal mesoporous carbon and the system thereof of a kind of iron content nickel bimetal Preparation Method, and utilize the application of dyestuff contaminant in the magnetic bimodal mesoporous carbon removal water of iron content nickel bimetal.
Background technology
Dyestuff contaminant is mainly derived from the discharge of the industrial wastewaters such as leather, printing and dyeing, pharmacy, food manufacturing, has higher Toxicity and stability, aquatile and ecosystem can be caused large effect, and be difficult to pass through by a small amount of environment that enters Self purification is removed in the environment, causes the research of its Degradation and Transformation method in recent years and pays close attention to widely.
At present, the active sludge of method of waste water from dyestuff, bioreactor, photocatalytic degradation, ion exchange etc. are processed Method.But these methods all exist, and operating process is loaded down with trivial details, there may be secondary pollution problems.In numerous removal water, dyestuff is dirty In the method for dye thing, absorption method is a kind of relatively simple, efficient and economic minimizing technology.The adsorbent such as activated carbon, zeolite has There are economy, easy feature, but they mostly have microcellular structure, limit answering in terms of absorption macromole dyestuff contaminant With.Meanwhile, these adsorbing materials there is also the shortcomings such as efficiency is low, heat stability is low.New Type of Mesoporous material regular has owing to having Sequence mesopore orbit structure and the feature such as huge specific surface area and pore volume, be a kind of excellent adsorbent.
With other isolation technics as filtered, centrifugal etc. compared with, magnetic separation technique has the advantages such as efficient, easy.At present The magnetic mesoporous carbon material of preparation only supports a kind of metal material, and the aperture of magnetic mesoporous material is also single aperture simultaneously, inhales Attached capacity is less, and magnetic is the strongest simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that a kind of specific surface area greatly, carry on a shoulder pole simultaneously Carrying iron-nickel alloy nano-particle, even particle distribution, the iron content nickel being difficult to reunite, magnetic performance is excellent and adsorption capacity is bigger are double The magnetic bimodal mesoporous carbon of metal, additionally provides a kind of easy and simple to handle, low cost, does not produce the double gold of iron content nickel of harmful by-products The preparation method of the magnetic bimodal mesoporous carbon belonged to, and the magnetic bimodal mesoporous carbon of this iron content nickel bimetal dye in removing water body Application in material pollutant, this application process has that adsorption capacity is big, removal efficiency is high, wide accommodation, easy and simple to handle, practical Property the advantage such as strong.
For solve the problems referred to above, the present invention by the following technical solutions:
Provide the magnetic bimodal mesoporous carbon of a kind of iron content nickel bimetal, the magnetic bimodal mesoporous of aforementioned iron content nickel bimetal Carbon is with magnetic bimodal mesoporous carbon as carrier, and iron-nickel alloy nano-particle is dispersed in magnetic bimodal mesoporous carbon the double gold of formation iron content nickel The magnetic bimodal mesoporous carbon belonged to；The aperture of the magnetic bimodal mesoporous carbon of iron content nickel bimetal be respectively 4nm～5nm and 15nm～ 20nm。
Further, the specific surface area of the magnetic bimodal mesoporous carbon of aforementioned iron content nickel bimetal is 1000m2/ g～1100m2/ G, the particle diameter of aforementioned iron-nickel alloy nano-particle is 10nm～20nm.
As total technology design, present invention also offers bimodal Jie of magnetic of a kind of aforesaid iron content nickel bimetal The preparation method of hole carbon, comprises the following steps:
S1, ferrum nitrate, nickel nitrate, furfuryl alcohol are mixed with ethanol, obtain complex solution；
S2, aforementioned complex solution is penetrated into by incipient wetness impregnation method SBA-15 mesoporous silicon template obtains be impregnated with polynary The mesoporous silicon template of solution, obtains complex by the aforementioned mesoporous silicon template being impregnated with complex solution by cured；
S3, aforesaid compounds is carried out in protective gas heat treatment, then through sodium hydroxide Adsorption silicon template, Magnetic bimodal mesoporous carbon to aforementioned iron content nickel bimetal.
Further, in aforementioned S1 step, aforementioned ferrum nitrate is Fe (NO3)3·9H2O, aforementioned nickel nitrate is Ni (NO3)2·6H2O, aforementioned ferrum nitrate, the molal weight ratio of nickel nitrate are 1: 1.
Further, in aforementioned S2 step, the volume mass ratio of aforementioned complex solution and aforementioned SBA-15 mesoporous silicon template For 1.4mL～1.6mL: 1.2g；Said curing process detailed process is: the aforementioned mesoporous silicon template being impregnated with complex solution existed 70 DEG C～air set 10h of 80 DEG C～12h.
Further, in abovementioned steps S3, aforementioned protective gas is the argon containing 5% hydrogen；The temperature of aforementioned heat treatment Being 800 DEG C～900 DEG C, the time of heat treatment is 2h～3h.
Further, aforementioned SBA-15 mesoporous silicon template uses following methods to prepare:
By poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer with tetraethyl orthosilicate at 30 DEG C～35 Mix and blend 18h～24h at a temperature of DEG C, obtains mixed liquor；By aforementioned mixed liquor hydro-thermal reaction 20h at 135 DEG C～140 DEG C ～24h, obtain white precipitate；Filter after aforementioned white washing of precipitate to neutrality, be dried, at a temperature of 500 DEG C～550 DEG C Aforementioned SBA-15 mesoporous silicon template is obtained after calcining 4h～6h.
As total technology design, present invention also offers bimodal Jie of magnetic of a kind of aforesaid iron content nickel bimetal The magnetic bimodal mesoporous carbon of the iron content nickel bimetal that hole carbon or aforesaid preparation method prepare is removing dyes dirt Application in dye thing, comprises the following steps:
Being joined by the magnetic bimodal mesoporous carbon of aforementioned iron content nickel bimetal containing in aqueous dye solutions, every milliliter aforementioned containing dye The magnetic bimodal mesoporous carbon of the aforementioned iron content nickel bimetal added in material aqueous solution, no less than 0.2mg, carries out constant temperature and shakes after mixing Swing reaction, Magnetic Isolation, complete the removal to dyes pollutant.
Further, every milliliter of aforementioned magnetic bimodal mesoporous containing the aforementioned iron content nickel bimetal added in aqueous dye solutions Carbon 0.2mg～0.5mg is aforementioned is 50mg/L～800mg/L containing the initial concentration of dyestuff in aqueous dye solutions.
Further, the aforementioned pH value containing aqueous dye solutions is 3.0～10.0, and the temperature of aforementioned constant temperature oscillation reaction is 25 DEG C～45 DEG C, rotating speed is 100rpm～150rpm, and the time is 2h～20h；Abovementioned dyes is methylene blue, methyl orange, rhodamine One or more in B, bright orange and active red.
Compared with prior art, the invention have the advantage that
(1) iron-nickel alloy is supported on magnetic bimodal mesoporous carbon by the application, makes magnetic bimodal mesoporous carbon have ratio mostly Count the magnetic performance that the magnetic mesoporous carbon of the single metal of load is more excellent, be possible not only to the adsorptivity utilizing mesoporous material excellent Can, the magnetic of magnetic nanoparticle can be utilized, it is possible to achieve the separation quick, easy to pollutant simultaneously.There is ratio simultaneously Surface area is big, iron-nickel alloy nano-particle is evenly distributed, and is difficult to the advantages such as reunion, magnetic performance excellence, and stable in physicochemical property.
(2) present invention uses incipient wetness impregnation method to prepare aperture and is respectively the double gold of iron content nickel of 4nm～5nm and 15nm～20nm The magnetic bimodal mesoporous carbon belonged to, in preparation process, a part of duct of silicon template is not filled, when removing silicon template, these The duct not being filled is connected with each other, and forms two grades of meso-hole structures.Owing to the macromolecule contaminants such as dyestuff are easily at micropore canals Internal congestion, two grades of mesoporous pore size are distributed near 18nm, are more beneficial for the diffusion of dyestuff, and therefore, magnetic prepared by the present invention is double Peak mesoporous carbon has higher adsorption capacity.
(3) preparation method of the magnetic bimodal mesoporous carbon of iron content nickel bimetal of the present invention uses mesoporous silicon template, by just Wet impregnation method one-step synthesis, preparation process is simple, and technology maturation does not produce harmful by-products.
(4) present invention utilizes the magnetic bimodal mesoporous carbon removal dyestuff contaminant of iron content nickel bimetal, can avoid being centrifuged, mistake The loaded down with trivial details operating process such as filter, the magnetic performance utilizing material excellent can realize sharp separation under the effect of external magnetic field. Adsorption efficiency is high, can reach adsorption equilibrium in 2h；Adsorption capacity is the most excellent, wide accommodation, in different pH value, temperature All can realize the active adsorption to multiple dyestuff contaminant down.Have that adsorption capacity is big, removal efficiency is high, wide accommodation, behaviour Make the advantages such as easy, practical.
Accompanying drawing explanation
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below in conjunction with the embodiment of the present invention In accompanying drawing, the technical scheme in the embodiment of the present invention is carried out clear, complete description.
Fig. 1 is the transmission electron microscope picture of the magnetic bimodal mesoporous carbon of the iron content nickel bimetal that embodiment 1 prepares.
Fig. 2 is nitrogen adsorption-desorption curve figure and the aperture of the magnetic bimodal mesoporous carbon of iron content nickel bimetal in embodiment 1 Scattergram.
Fig. 3 be the magnetic bimodal mesoporous carbon of the iron content nickel bimetal in embodiment 2 under different pH condition to methylene The blue adsorption capacity with methyl orange.
Fig. 4 be the magnetic bimodal mesoporous carbon of the iron content nickel bimetal in the embodiment of the present invention 3 when different time to methylene The blue adsorption capacity with methyl orange of base.
Detailed description of the invention
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but the most therefore and Limit the scope of the invention.
Material and instrument employed in following example are commercially available.
Embodiment 1
A kind of magnetic bimodal mesoporous carbon of the iron content nickel bimetal of the present invention, the magnetic bimodal mesoporous of this iron content nickel bimetal Carbon is with magnetic bimodal mesoporous carbon as carrier, and iron-nickel alloy nano-particle is dispersed in magnetic bimodal mesoporous carbon and forms orderly bimodal Jie Pore structure, two peak values of pore-size distribution respectively appear near 4nm and near 18nm, the wherein grain of iron-nickel alloy nano-particle Footpath is 10nm～20nm.
The preparation method of the magnetic bimodal mesoporous carbon of the iron content nickel bimetal of a kind of above-mentioned the present embodiment, including following step Rapid:
1, mesoporous silicon template is prepared:
1-1, first by 4.0g poly(ethylene oxide)-poly(propylene oxide)-polyethylene oxide block copolymer P123 (Sigma Producing, molecular weight is 5800) it is placed in the HCl that 160ml concentration is 1.5M, add 8.5g tetraethyl orthosilicate (TEOs), at 30 DEG C ～mix and blend 22h (mixing time is that 18h～24h all can implement) at a temperature of 35 DEG C, obtain mixed liquor.
1-2, by mixed liquor at 135 DEG C～140 DEG C hydro-thermal reaction 24h (the hydro-thermal reaction time is that 20h～24h all can be real Execute), obtain white precipitate.
1-3, by white precipitate washing to filtering after neutrality, air-dry under room temperature, obtain white powder after drying；By white powder End is put in batch-type furnace, and controlling heating rate is l DEG C/min, and (calcination time is to calcine 4h at a temperature of 500 DEG C～550 DEG C 4h～6h all can implement), ground i.e. obtain SBA-15 mesoporous silicon template.
2, by the Fe (NO of ferrum nitrate 0.8mmol3)3·9H2Ni (the NO of O and 0.8mmol3)2·6H2O is dissolved in 0.5mL In ethanol, under agitation add 1mL furfuryl alcohol, form complex solution；Extraction 1.5mL complex solution, penetrates into by incipient wetness impregnation method In the SBA-15 mesoporous silicon template of 1.2g, (volume mass of complex solution and SBA-15 mesoporous silicon template is than for 1.4mL～1.6mL : 1.2g all can implement), then in the air of 80 DEG C, the mesoporous silicon template being impregnated with complex solution is solidified 12h (solidification temperature Be 70 DEG C～80 DEG C, hardening time be that 10h～12h all can implement), dried under room temperature, obtain complex.
3, the complex that step 2 is obtained in the argon containing 5% hydrogen at a temperature of 800 DEG C～900 DEG C at heat Reason 2h (heat treatment time is that 2h～3h all can implement), controlling heating rate is 2 DEG C/min, then with being heated to 80 DEG C～90 DEG C The sodium hydroxide solution that concentration is 2M wash twice, remove the SBA-15 mesoporous silicon template in complex, then carry out filtering, clearly It is washed till neutrality, is dried at a temperature of 70 DEG C, obtains the magnetic bimodal mesoporous carbon of iron content nickel bimetal.
The magnetic bimodal mesoporous carbon of prepared iron content nickel bimetal is carried out transmission electron microscope imaging, obtains as shown in Figure 1 Transmission electron microscope picture.In Fig. 1, orderly band is high-visible, shows magnetic bimodal mesoporous carbon order mesoporous of iron content nickel bimetal Structure is without destruction, meanwhile, is dispersed in inside duct on a large scale, the stain on surface is then for ferrum nickle duplex metal nano granule.
The magnetic bimodal mesoporous carbon of prepared iron content nickel bimetal is placed in full-automatic specific surface area analysis instrument, carries out nitrogen Aspiration is attached-resolve experiment, draw absorption-desorption isothermal line (seeing Fig. 2), and it is bimodal that two hysteretic loops in Fig. 2 indicate magnetic The existence of two kinds of meso-hole structures in mesoporous carbon；With total particle diameter distribution of BJH model estimation magnetic bimodal mesoporous carbon, obtain such as Fig. 2 Grain size distribution shown in interior illustration, and the pore-size distribution peak value understanding the magnetic bimodal mesoporous carbon of iron content nickel bimetal mainly goes out Now near 4nm and near 18nm, (4nm near zone particularly relates to the main integrated distribution in the aperture pore diameter range at 4nm～5nm In, 18nm near zone particularly relates to the main integrated distribution in aperture in the pore diameter range of 15nm～20nm), record saturated magnetization Value is 12.4emu/g, shows that the magnetic of the magnetic bimodal mesoporous carbon of iron content nickel bimetal can be applicable to Magnetic Isolation.
Calculate the specific surface area of the magnetic bimodal mesoporous carbon of iron content nickel bimetal by BET method, show that specific surface area is 1058.7m2/g。
Comparative example 1
A kind of magnetic mesoporous carbon Han Fe, with magnetic mesoporous carbon as carrier, iron nano-particle is dispersed in shape in magnetic mesoporous carbon Become ordered mesopore structure.Its preparation method is except the Fe (NO only adding 1.6mmol in step 23)3·9H2Outside O, remaining step and reality Execute example 1 identical.
Comparative example 2
A kind of magnetic mesoporous carbon Han Ni, with magnetic mesoporous carbon as carrier, nano nickel particles is dispersed in shape in magnetic mesoporous carbon Become ordered mesopore structure.Its preparation method is except the Ni (NO only adding 1.6mmol in step 23)2·6H2Outside O, remaining step and reality Execute example 1 identical.
By the magnetic bimodal mesoporous carbon of the iron content nickel bimetal of embodiment 1, comparative example 1 containing Fe magnetic mesoporous carbon and contrast Example 2 carry out saturation magnetisation value detection containing Ni magnetic mesoporous carbon, testing result is shown in Table 1.
The saturation magnetisation value of the table 1 magnetic mesoporous carbon containing different metal
As shown in Table 1, the magnetic bimodal mesoporous carbon containing ferrum nickel bimetal of the present invention has than the magnetic containing single metal The property higher saturation magnetisation value of mesoporous carbon.
Embodiment 2
A kind of magnetic bimodal mesoporous carbon utilizing the iron content nickel bimetal prepared in embodiment 1 is removing water Methylene Blue With the application in methyl orange, its application process specifically includes following steps:
(1) prepare respectively 8 groups of 25mL concentration be 150mg/L containing aqueous solution of methylene blue, and regulate pH value be respectively 3, 4,5,6,7,8,9 and 10.Prepare the aqueous solution containing methyl orange that 8 groups of 25mL concentration is 150mg/L the most respectively, And regulate pH value and be respectively 3,4,5,6,7,8,9 and 10.
(2) often organizing the magnetic bimodal mesoporous carbon all adding 5mg iron content nickel bimetal in solution, 25 DEG C, 150rpm turns Under the conditions of speed after vibration absorption 2h, through external magnetic field Magnetic Isolation, complete the removal to dyes pollutant.
Then recycling ultraviolet spectrophotometer measures and remains methylene blue or the content of methyl orange in solution, and calculating contains The magnetic bimodal mesoporous carbon of the ferrum nickel bimetal adsorption capacity to two kinds of dyestuffs, experimental result is as shown in Figure 3.
From the figure 3, it may be seen that the magnetic bimodal mesoporous carbon of iron content nickel bimetal to the adsorption capacity of methylene blue along with pH value Increase and increase, the adsorption capacity of methyl orange is reduced with the growth of pH value.But, in the pH value range studied, should The magnetic bimodal mesoporous carbon of iron content nickel bimetal all has higher adsorption capacity for two kinds of dyestuffs, shows the double gold of this iron content nickel The pH value range that the magnetic bimodal mesoporous carbon belonged to adapts to is wider.
Embodiment 3
A kind of magnetic bimodal mesoporous carbon utilizing the iron content nickel bimetal prepared in embodiment 1 is removing water Methylene Blue With the application in methyl orange, its application process specifically includes following steps:
Prepare respectively 25mL concentration be the aqueous solution containing methyl orange of 150mg/L, 25mL concentration be 150mg/L containing methylene The aqueous solution that base is blue, the pH value regulating two groups of aqueous solutions is 7.The magnetic being then respectively adding 5mg iron content nickel bimetal is bimodal Mesoporous carbon in two groups of aqueous solutions, 25 DEG C, vibration absorption 15min under 150rpm speed conditions, 30min, 1h, 1.5h, 2h, After 3h, 5h, 10h, 20h, through external magnetic field Magnetic Isolation, complete the removal to dyes pollutant.
Utilize ultraviolet spectrophotometer to measure in solution and remain methylene blue and the content of methyl orange, and it is double to calculate iron content nickel The magnetic bimodal mesoporous carbon of the metal adsorption capacity to two kinds of dyestuffs, experimental result is as shown in Figure 4.
As shown in Figure 4, methylene blue and methyl orange are gone by the magnetic bimodal mesoporous carbon of the iron content nickel bimetal of the present invention Removal rates is fast, and adsorption capacity during 1h can reach the 80% of equilibrium adsorption capacities, can realize adsorption equilibrium during 2h.Therefore, The magnetic bimodal mesoporous carbon of this iron content nickel bimetal can be applicable to the dyestuff contaminant quickly removing in water.
Embodiment 4
A kind of magnetic bimodal mesoporous carbon utilizing the iron content nickel bimetal prepared in embodiment 1 is removing water Methylene Blue With the application in methyl orange, its application process specifically includes following steps:
Prepare 8 groups of volumes respectively and be 25mL, concentration is respectively 50,100,200,300,400,500,600,800mg/L, The aqueous solution containing methyl orange, 8 groups of volumes are 25mL；Concentration is respectively 50,100,200,300,400,500,600, The aqueous solution containing methylene blue of 800mg/L.It is 7 that the pH value of aqueous solution is often organized in regulation, is then respectively adding 5mg embodiment 1 The magnetic bimodal mesoporous carbon of iron content nickel bimetal, 25 DEG C～45 DEG C, under 150rpm speed conditions after vibration absorption 2h, through outside Magnetic field separates, and completes the removal to dyes pollutant.
Utilize ultraviolet spectrophotometer to measure in solution and remain methylene blue or the content of methyl orange, and according to Lang Gemiaoer Tellurium determination (1) calculates the magnetic bimodal mesoporous carbon of the iron content nickel bimetal theory high-adsorption-capacity to two kinds of dyestuffs, Experimental result is as shown in table 2.
q e = q m b C e 1 + bC e - - - ( 1 )
Wherein qeFor equilibrium adsorption capacities (mg/g), CeFor the concentration (mg/L) of methylene blue or methyl orange, qmFor theory Good adsorption capacity (mg/g), and b is adsorption equilibrium costant (L/mg).
The magnetic bimodal mesoporous carbon adsorption dyestuff Lang Gemiaoer adsorption isotherm mould of iron content nickel bimetal during table 2 different temperatures Shape parameter
As shown in Table 2, the magnetic bimodal mesoporous carbon of iron content nickel bimetal to the adsorption capacity of two kinds of dyestuffs along with dyestuff The increase of initial concentration and increase, meanwhile, the rising of solution temperature is conducive to this adsorbent to remove dyestuff contaminant.Result table Bright, this adsorbent adaptable dyestuff initial concentration scope and temperature range are relatively wide, under higher dyestuff initial concentration and different Remain under temperature conditions realize effectively removing.
Embodiment 5:
A kind of magnetic bimodal mesoporous carbon dye discoloration in removing water utilizing the iron content nickel bimetal prepared in embodiment 1 Application in thing, comprises the following steps:
Prepare the aqueous solution containing 500mg/L methylene blue respectively, containing the aqueous solution of 500mg/L methyl orange, containing sieve 500mg/L The aqueous solution of red bright B, containing aqueous solution bright orange for 500mg/L and the aqueous solution containing 500mg/L active red, each 25mL.Regulate often group The pH value of aqueous solution is 7, is separately added into the magnetic bimodal mesoporous carbon of 5mg iron content nickel bimetal, 25 DEG C, 150rpm speed conditions After lower vibration absorption 2h, through external magnetic field Magnetic Isolation, complete the removal to dyes pollutant.
Meanwhile, in order to contrast bimodal mesoporous carbon and the absorption property of unimodal mesoporous carbon, add 5mg magnetic after the same method The unimodal mesoporous carbon of property (Fe/CMK-3), the specific surface area of the unimodal mesoporous carbon of magnetic is 679.4m2/ g, pore volume is 0.81cm3/ g, hole Footpath is 3.8nm.Contrast with the magnetic bimodal mesoporous carbon of iron content nickel bimetal, investigate it and dyes pollutant are gone Except efficiency.
Utilize ultraviolet spectrophotometer to measure the content of excess dye in each group of aqueous solution, and calculate iron content nickel bimetal The magnetic bimodal mesoporous carbon adsorption capacity to five kinds of dyestuffs, comparing result is as shown in table 3.
The magnetic bimodal mesoporous carbon of table 3 iron content nickel bimetal and the magnetic unimodal mesoporous carbon adsorption capacity to multiple dyestuff
As shown in Table 3, the magnetic bimodal mesoporous carbon of this iron content nickel bimetal is to methylene blue and the adsorption capacity of methyl orange Higher, and its three kinds of dyestuff contaminants all have higher adsorption capacity, show the magnetic bimodal mesoporous of this iron content nickel bimetal Carbon can be efficiently applied to the removal of multiple dyestuff contaminant.Meanwhile, the magnetic bimodal mesoporous carbon of iron content nickel bimetal is to five kinds of dyes The adsorption capacity of material, apparently higher than the unimodal mesoporous carbon of magnetic (Fe/CMK-3), shows that magnetic bimodal mesoporous carbon has more mesoporous than unimodal The absorption property that carbon is the most excellent.
In embodiment 2 to 5, the addition of the magnetic bimodal mesoporous carbon of iron content nickel bimetal be 0.2mg/mL be only minimum Addition, in actual application process, by increasing the addition of the magnetic bimodal mesoporous carbon of iron content nickel bimetal, as 0.2mg/mL～0.5mg/mL, can reach more preferably technique effect.
During constant temperature oscillation, the temperature of constant temperature oscillation reaction is 25 DEG C～45 DEG C, and rotating speed is 100rpm～150rpm, Time is 2h～20h, all can implement.
The above, be only presently preferred embodiments of the present invention, and the present invention not makees any pro forma restriction.Though So the present invention discloses as above with preferred embodiment, but is not limited to the present invention.Any it is familiar with those skilled in the art Member, in the case of without departing from the spirit of the present invention and technical scheme, may utilize in method and the technology of the disclosure above Hold and technical solution of the present invention is made many possible variations and modification, or be revised as the Equivalent embodiments of equivalent variations.Therefore, Every content without departing from technical solution of the present invention, according to the present invention technical spirit to made for any of the above embodiments any simply Amendment, equivalent, equivalence change and modification, all still fall within the range of technical solution of the present invention protection.

Claims (6)

1. the magnetic bimodal mesoporous carbon of an iron content nickel bimetal application in removing dyes pollutant, its feature exists In, comprise the following steps:
The magnetic bimodal mesoporous carbon of described iron content nickel bimetal is joined containing in aqueous dye solutions, the water Han dyestuff described in every milliliter Magnetic bimodal mesoporous carbon 0.2 mg～0.5 mg of the described iron content nickel bimetal added in solution, carries out constant temperature oscillation after mixing Reaction, Magnetic Isolation, complete the removal to dyes pollutant；Described containing the initial concentration of dyestuff in aqueous dye solutions it is 50 mg/L～800 mg/L；The described pH value containing aqueous dye solutions is 3.0～10.0, and the temperature of described constant temperature oscillation reaction is 25 DEG C～45 DEG C, rotating speed is 100 rpm～150 rpm, and the time is 2 h～20 h；Described dyestuff be methylene blue, methyl orange, One or more in rhodamine B, bright orange and active red；
The magnetic bimodal mesoporous carbon of described iron content nickel bimetal is with magnetic bimodal mesoporous carbon as carrier, and iron-nickel alloy nano-particle divides Being dispersed in magnetic bimodal mesoporous carbon the magnetic bimodal mesoporous carbon forming iron content nickel bimetal, the magnetic of described iron content nickel bimetal is double The aperture of peak mesoporous carbon is respectively 4 nm～5 nm and 15 nm～20 nm；The magnetic bimodal mesoporous carbon of described iron content nickel bimetal Specific surface area be 1000 m2/ g～1100 m2/ g, the particle diameter of described iron-nickel alloy nano-particle is 10 nm～20 nm.
Application the most according to claim 1, it is characterised in that the system of the magnetic bimodal mesoporous carbon of described iron content nickel bimetal Preparation Method, comprises the following steps:
S1, ferrum nitrate, nickel nitrate, furfuryl alcohol are mixed with ethanol, obtain complex solution；
S2, described complex solution is penetrated in SBA-15 mesoporous silicon template by first wet osmosis obtain being impregnated with complex solution Mesoporous silicon template, the described mesoporous silicon template being impregnated with complex solution is obtained complex by cured；
S3, described complex is carried out in protective gas heat treatment, then through sodium hydroxide Adsorption silicon template, obtain institute State the magnetic bimodal mesoporous carbon of iron content nickel bimetal.
Application the most according to claim 2, it is characterised in that described in described S1 step, ferrum nitrate is Fe(NO3)3· 9H2O, described nickel nitrate is Ni(NO3)2·6H2O, described ferrum nitrate, the mol ratio of nickel nitrate are 1: 1.
Application the most according to claim 2, it is characterised in that in described S2 step, described complex solution and described SBA- The volume mass ratio of 15 mesoporous silicon templates is 1.4 mL～1.6 mL: 1.2 g；Described cured detailed process is: by described It is impregnated with air set 10 h～12 h that the mesoporous silicon template of complex solution is at 70 DEG C～80 DEG C.
Application the most according to claim 2, it is characterised in that protective gas described in described step S3 is containing 5% hydrogen Argon；The temperature of described heat treatment is 800 DEG C～900 DEG C, and the time of heat treatment is 2 h～3 h.
6. according to the application described in any one of claim 2 to 5, it is characterised in that described SBA-15 mesoporous silicon template use with Lower section method prepares:
By poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer with tetraethyl orthosilicate at 30 DEG C～35 DEG C At a temperature of mix and blend 18 h～24 h, obtain mixed liquor；By described mixed liquor hydro-thermal reaction 20 h at 135 DEG C～140 DEG C ～24 h, obtain white precipitate；Filter after described white precipitate washing to neutrality, be dried, 500 DEG C～the temperature of 550 DEG C Described SBA-15 mesoporous silicon template is obtained after lower calcining 4 h～6 h.
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