CN109589928A - A kind of composite material and preparation method and application of load iron - Google Patents
A kind of composite material and preparation method and application of load iron Download PDFInfo
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- CN109589928A CN109589928A CN201710924210.3A CN201710924210A CN109589928A CN 109589928 A CN109589928 A CN 109589928A CN 201710924210 A CN201710924210 A CN 201710924210A CN 109589928 A CN109589928 A CN 109589928A
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- 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
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- B01J20/26—Synthetic macromolecular 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
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Abstract
The invention discloses the composite material of load iron, the composite material has iron using carbon material as carrier, in supported on carriers.The composite material can be prepared by the following method: carbon source and source of iron be mixed, stirring is calcined after dry, and then obtains the composite material of load iron.The composite material is not easy to reunite and is oxidized, large specific surface area, and reactivity is high, and preparation method is easy, and raw material is easy to get.
Description
Technical field
The present invention relates to sewage treatment field, in particular to a kind of composite material and preparation method of load iron and answer
With.
Background technique
With industrial fast development in recent years, the energy and problem of environmental pollution are constantly subjected to the generally pass of people
Note.In pollutant effluents processing, organic dyestuff is one of main pollution, and dyestuff not only has specific color, and structure
Complexity, be with high-molecular complex it is more, structure is difficult to be broken, and biological degradability is lower, mostly all have genotoxic potential, in ring
Returning in border becomes dependent on many unknown factors, in addition DYE PRODUCTION have the characteristics that it is wide in variety, in batches less, updating decision, cause
Waste water from dyestuff difficulty finds effective processing method, rhodamine B especially therein, is one of most common pollutant,
And rhodamine B was used as food additive, rear research is the discovery that the carcinogen being harmful to the human body, and threatens human health.
For common iron powder, nano zero valence iron has the advantages that large specific surface area, reactivity is high, and partial size is small,
The multiple pollutant in soil and water body environment can be fast and effeciently removed, therefore receives the extensive pass of various circles of society recently
Note.However, nano zero valence iron is but very limited system in actual application, there are some problems: easy to reunite to make it at bulky grain
Dispersibility is poor, is settled due to gravity, and stability is poor, not easy to maintain in air, can be oxidized rapidly, this
Significantly reduce the use utilization rate of nano zero valence iron.
Therefore, need to develop it is a kind of it is low in cost, preparation method is easy, not easy to reunite and not oxidized composite material and
Preparation method.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that: carbon source and source of iron are mixed, stirred
It mixes, is calcined after dry, and then obtain the composite material of load iron, the composite material is not easy to reunite and is not easy to be oxidized, than
Surface area is big, and reactivity is high, so as to complete the present invention.
The purpose of the present invention is to provide following aspect:
In a first aspect, providing a kind of composite material of load iron, the composite material is using carbon material as carrier, on carrier
Load has iron.
The carbon material is active carbon or graphitized carbon, preferably graphitized carbon (PGC), it is preferable that provides the carbon materials
The carbon source of material is organic carbon source, preferably carboritride, more preferably melamine, dicyanodiamine, urea, in cyanamide
It is one or more, especially preferably melamine.
The iron is selected from one or more of iron simple substance and the compound of iron,
The iron simple substance is Zero-valent Iron, preferably nano-level iron,
The compound of the iron is the oxide of iron or the carbide of iron, the preferably oxide of iron,
It is highly preferred that the mode of the carbon material supported iron be it is embedded, the mode that preferably chemical bond is crossed by Tie Tong is embedded in carbon
In skeleton.
Second aspect provides a kind of method of the composite material of load iron described above, the described method comprises the following steps:
Step (1) mixes carbon source and source of iron；
Step (2), the mixture that step (1) is obtained are calcined, and the composite material of load iron is obtained.
The third aspect provides the application of the composite material of load iron described in first aspect or second aspect, especially locates
Manage the application in terms of organic dyestuff sewage.
The composite material of the load iron provided according to the present invention, has the advantages that
(1) composite material of load iron provided by the invention is not easy to reunite and is not easy to be oxidized, and stability is good, recycling
Property it is high, adsorption capacity is strong；
(2) present invention is successfully prepared the composite material of load iron, specific surface with higher by carbothermic method
Long-pending and void content；
(3) composite material of load iron provided by the invention for handle pollutant effluents, especially waste water from dyestuff have compared with
Good removal effect and good development prospect；.
(4) preparation method provided by the invention has easy to operate, and raw material is conventional, it is easy to accomplish the advantages of.
Detailed description of the invention
Fig. 1 shows the full spectrogram of XPS of sample made from embodiment 1；
Fig. 2 shows the Fe 2p spectrograms of sample made from embodiment 1；
Fig. 3 shows the C 1s spectrogram of sample made from embodiment 1；
Fig. 4 shows the O 1s spectrogram of sample made from embodiment 1；
Fig. 5 shows the XRD spectra of sample made from Examples 1 to 7 and comparative example 1~2
Fig. 6 shows the N of sample made from embodiment 12Adsorption/desorption (a) and pore size distribution curve figure (b)；
Fig. 7 shows the N of sample made from embodiment 22Adsorption/desorption (a) and pore size distribution curve figure (b)；
Fig. 8 shows the N of sample made from embodiment 32Adsorption/desorption (a) and pore size distribution curve figure (b)；
Fig. 9 shows the N of sample made from embodiment 42Adsorption/desorption (a) and pore size distribution curve figure (b)；
Figure 10 shows the N of sample made from embodiment 52Adsorption/desorption (a) and pore size distribution curve figure (b)；
Figure 11 shows the N of sample made from embodiment 62Adsorption/desorption (a) and pore size distribution curve figure (b)；
Figure 12 shows the N of sample made from embodiment 72Adsorption/desorption (a) and pore size distribution curve figure (b)；
Figure 13 shows the thermogravimetric curve of sample made from Examples 1 to 7；
Figure 14 shows sample made from Examples 1 to 7 to the removal efficiency of RhB；
Figure 15 shows (curve a), experiment 1 (4 curve b), experiment (curve c) before sample experiments made from embodiment 1
(the XRD diagram of curve d) after placing 15 days in air
Figure 16 shows (a), in air (b) and 4 times (c) of experiment after placement 15 days before sample experiments made from embodiment 1
Scanning electron microscope (SEM) photograph；
Figure 17 shows sample made from embodiment 1 and reuses 1,2,3 and 4 removal rate to RhB in solution；
It is respectively sample made from 3,5,7,9 pairs of embodiments 1 to RhB removal rate that Figure 18, which shows initial pH value,；
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.Here as " exemplary "
Illustrated any embodiment should not necessarily be construed as preferred or advantageous over other embodiments.Although each of embodiment is shown in the attached drawings
In terms of kind, but unless otherwise indicated, it is not necessary to attached drawing drawn to scale.
According to the first aspect of the invention, a kind of composite material of load iron is provided, the composite material is with carbon material
Carrier has iron in supported on carriers.
The carbon material is active carbon or graphitized carbon, preferably graphitized carbon (PGC), it is preferable that provides the carbon materials
The carbon source of material is organic carbon source, preferably carboritride, more preferably melamine, dicyanodiamine, urea, in cyanamide
It is one or more, especially preferably melamine.
Inventors have found that graphitized carbon is a kind of with antiscour, chipping resistance, the material of erosion resisting, ketjenblack EC
Surface hexagonal structure makes its molecule for planar molecule or containing plane aromatic rings have strong suction-operated, tool
Having the carbon material of graphite-structure effectively big in performance can improve, and can be used as a kind of good carrier material.
In the present invention, the iron is selected from one or more of iron simple substance and the compound of iron, is preferably selected from iron simple substance and iron
Compound,
The iron simple substance is Zero-valent Iron, preferably nano-level iron, more preferably nano zero valence iron,
The compound of the iron is the oxide of iron or the carbide of iron, the preferably oxide of iron, more preferably four oxygen
Change three-iron.
Inventors have found that nano zero valence iron has large specific surface area, it is excellent that reactivity is high, and partial size is small, reducing power is strong etc.
Point can fast and effeciently remove the multiple pollutant in soil and water body environment, be loaded on the carbon material, especially stone
On inkization carbon, loaded nano zeroth order iron complexes are prepared into enhance its dispersion stabilization, nano zero valence iron is avoided and easily rolls into a ball
Poly- and easy the problems such as being oxidized.
In the present invention, the mode of the carbon material supported iron is embedded, and the mode that preferably chemical bond is crossed by Tie Tong is embedded in
In carbon skeleton, the damascene structures are conducive to be promoted the reactivity and stability of composite material itself, are subtracted by steric effect
Reunion caused by the weak magnetism due to nano zero valence iron itself, so that the stability of composite material is fine, even in air
The preservation of short time is also not easy to be oxidized.
In the present invention, the specific surface area of the composite material is 50m2/ g~130m2/ g, preferably 80m2/ g~
128m2/ g, more preferably 126.04m2/ g,
Pore volume is 0.05cm3/ g~0.3cm3/ g, preferably 0.1cm3/ g~0.3cm3/ g, more preferably 0.3cm3/ g,
Porosity is 4nm~10nm, preferably 5nm~9.8nm, more preferably 9.67nm.
In the present invention, the composite material is 44.7 ° and 65.1 ° punishment in 2 θ of the angle of diffraction according to its XRD analysis
Not there is crystallographic plane diffraction peak.
Second aspect provides the preparation method of the composite material of load iron described in first aspect, and the method includes following
Step:
Step (1) mixes carbon source and source of iron；
In the present invention, the carbon source is organic carbon source, preferably carboritride, more preferably melamine, dicyan
One of diamines, urea, cyanamide are a variety of, especially preferably melamine.
In the present invention, the source of iron is molysite or ferrous salt, preferably molysite, more preferably iron chloride, ferric nitrate, sulphur
One of sour iron, ferric acetate, especially preferably iron chloride.
In the present invention, the molar ratio of the carbon source and source of iron is 5~10: 1, preferably 6~9: 1, more preferably 8: 1.
Inventors have found that the ratio that carbon source and source of iron is added all has an impact to the load capacity of iron and the structure of composite material,
When source of iron is molysite, relatively large meeting of additional amount so that iron salt hydrolysis produces sour more, reduce the composite material of load iron
The degree of order of structure, when additional amount is relatively small, the load capacity of iron is lower on composite material, and then influences the property of composite material
It can structure.
In one preferred embodiment, in solvent, the solvent is preferably for the carbon source and source of iron mixed dissolution
Water, more preferably deionized water.
In step of the present invention (1), mixed carbon source and source of iron are stirred at a certain temperature, preferably in water-bath item
It is carried out under part,
The temperature is 50 DEG C~90 DEG C, preferably 60 DEG C~85 DEG C, more preferably 80 DEG C, in order to the control of reaction condition
System and operation, so that carbon source and source of iron are sufficiently mixed uniformly,
The stirring can be excellent using any one agitating mode in the prior art, such as the stirring of magnetic agitation, glass bar
Magnetic agitation is selected as,
Mixing time is conducive to iron uniform load in carbon so that carbon source and source of iron are sufficiently mixed for 1h~3h, preferably 2h
On material, do not reunite, and then obtains the good composite material of structure and morphology.
In one preferred embodiment, mixed solution is dry, special limit is not done to drying mode used
It is fixed, can be using any one drying mode in the prior art, such as normal temperature and pressure is dry, room temperature is dried under reduced pressure, it is preferable that make
It being dried with baking oven, dry temperature is 100 DEG C~150 DEG C, preferably 100 DEG C~120 DEG C, more preferably 100 DEG C, so that
It obtains solution to be completely dried, removes moisture removal, and then shorten calcination time, do not influence the structure of composite material in calcining.
Step (2), the mixture that step (1) is obtained are calcined, and the composite material of load iron is obtained.
In one preferred embodiment, the calcining carries out under the atmosphere for being passed through inert gas, is preferably calcining
Start to be passed through inert gas before, further, it is preferable to be passed through inert gas 8min~25min before being calcined, more preferably
15min。
Preferably, the flow of inert gas be 30mL/min~70mL/min, preferably 40mL/min~60mL/min, more
Preferably 50mL/min.
In one preferred embodiment, the temperature of the calcining be 680 DEG C~1000 DEG C, preferably 700 DEG C~900
DEG C, more preferably 700 DEG C.
In the present invention, calcination temperature plays vital shadow to performances such as appearance structure, the stability of composite material
It rings, do not include when calcination temperature is lower than 680 DEG C, in composite material or only contains micro nano iron oxide, when calcining temperature
When spending high, iron aggravates the graphitizing of carbon material under the contraction and high temperature due to carbon material itself, leads to carbon structure
It shrinks, may cause the collapsing of pore structure, or even lose activity, inventors have found that when calcination temperature is 700 DEG C, it is obtained
The specific surface area of sample is maximum, and the structure of composite material is not damaged, and has high porosity.
1h~4h, preferably 1.5h~3h, more preferable 2h are kept the temperature at calcination temperatures.
Preferably, calcination temperature is warming up to by certain heating rate, the heating rate be 3 DEG C/min~10 DEG C/
Min, preferably 4 DEG C/min~8 DEG C/min, more preferably 5 DEG C/min.
Inventors have found that heating rate is very fast, the pore structure of carbon material can be destroyed to a certain extent, even more so that hole is tied
Structure collapses, and the degree of order of material is caused to reduce；Heating rate is excessively slow, and the porosity that will lead to carbon material is low, and specific surface area is low.
In one preferred embodiment, after calcining, cooling obtains the composite material of load iron, to the drop
Warm mode is not specially limited, preferably Temperature fall, further, it is preferable to be cooled to 20 DEG C~50 DEG C, is more preferably cooled to 20
DEG C~30 DEG C.
In step (2), the composite material of obtained load iron has iron using carbon material as carrier, in supported on carriers, preferably
The mode that chemical bond is crossed by Tie Tong is embedded in carbon skeleton,
It is to be respectively present crystallographic plane diffraction peak at 44.7 ° and 65.1 ° in 2 θ of the angle of diffraction according to its XRD analysis.
The third aspect is especially located according to the application of first aspect or the composite material of the load iron of second aspect offer
Manage the application in terms of organic dyestuff sewage.
Embodiment
Embodiment 1
Using melamine as carbon source, iron chloride (FeCl3) it is used as source of iron, according to melamine and FeCl3Molar ratio is 8:
1 ratio mixing, is dissolved in 100mL deionized water, and then magnetic agitation 2h mixes it uniformly under 80 DEG C of water bath conditions,
Obtained solution is put into 100 DEG C of baking ovens and is completely dried moisture removal；
The brown mixture obtained after drying is placed in quartz boat, is subsequently placed into the heated at constant temperature portion of tubular type Muffle furnace
Position, is passed through 15min N2Interior remaining air, N are managed with removal2Flow is 50mL/min, then in N2Under atmosphere, with 5 DEG C/min
Heating rate be warming up to 700 DEG C calcining and constant temperature 2h, carry out high temperature cabonization reduction, be then allowed to stand Temperature fall, to temperature drop
It is taken out to 30 DEG C or less, obtains Fe/Fe3O4/ PGC composite material；
The XPS spectrum figure of products therefrom is as shown in figures 1-4, wherein
Fig. 1 shows the full spectrogram of XPS of sample made from embodiment 1；
Fig. 2 shows the Fe 2p spectrograms of sample made from embodiment 1；
Fig. 3 shows the C 1s spectrogram of sample made from embodiment 1；
Fig. 4 shows the O 1s spectrogram of sample made from embodiment 1；
As shown in Figure 1, there are four peaks of C, N, O, Fe in figure, and wherein about in 284ev, the peak N 1s about exists at the peak C 1s
About in 530ev, the peak Fe 2p illustrates that nano zero valence iron is successfully embedded into graphitized carbon about in 710ev at the peak 289ev, O 1s
Skeleton in.
As shown in Fig. 2, the XPS spectrum figure of Fe 2p is divided into the Fe 2p of low-lying level3/2With the Fe 2p of high level1/2Two are not
Symmetrical part, this is mainly due to caused by spin orbit splitting, wherein nanometer can be had in the explanation of peak 706.7ev at by combining
The presence of Zero-valent Iron (nZVI), Fe2+2p3/2And Fe3+2p3/2Combination can peak about in 709ev and 711ev, and Fe2+2p1/2With
Fe3+2p1/2Combination can peak be located at 720.2ev and 724.1ev, illustrate in material contain ferrous iron and ferric iron, it was demonstrated that have
Fe3O4Presence.
As shown in figure 3, C 1s spectrogram can be broken down into two parts: graphitized carbon (284.7ev) and C-O
(286.7ev)；
As shown in figure 4, O 1s spectrogram can be broken down into three parts: oxygen physisorption (530.6ev), Fe-O
(531ev) and C=O, O-C=O (532.2ev), wherein Fe-O functional group there are surface, there are the oxides of iron.
Embodiment 2~7
2~7 method therefor of embodiment is similar to Example 1, and difference is only that calcination temperature is respectively 750 DEG C, and 800 DEG C,
It 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, obtains being Fe/Fe3C/PGC composite material.
The XRD of product made from embodiment 2~7 is as described in experimental example 1.
Comparative example
Comparative example 1~2
1~2 method therefor of comparative example is similar to Example 1, and difference is only that calcination temperature is respectively 600 DEG C and 660 DEG C.
Experimental example
Experimental example 1
The XRD spectra of sample
The present embodiment sample used is made by Examples 1 to 7 and comparative example 1~2.
To sample obtained carry out XRD spectra measurement, as a result as shown in Fig. 2,
Fig. 5 shows the XRD spectra (distribution homologous thread a~g) of sample made from Examples 1 to 7 and comparative example 1~2 is made
The XRD spectra (respectively corresponding curve h~i) of the sample obtained；
As shown in Figure 5, there is many small miscellaneous peaks in sample made from comparative example 1~2, it is not easy to go out it in clearly differentiating
The crystal phase that middle substance contains；
And from the sample that Examples 1 to 7 obtains, it can be found that sample is respectively from 44.7 ° and 65.1 °, there are relatively strong
Strong diffraction maximum illustrates obtained sample all α-Fe (JCPDS, No.87-0722) containing body-centered cubic structure；
It can be found that there are apparent diffraction maximum is right respectively at 43.7 ° and 44.1 ° in the sample that embodiment 2~7 obtains
That answer is Fe3(102) of C, the characteristic peak (JCPDS, No.89-2867) of (220)；
In addition, there is the Fe containing face-centred cubic structure at 35.5 ° in the sample that embodiment 1 obtains3O4(JCPDS
Card No.75-1609) diffraction maximum, illustrate that this sample is with Fe/Fe3O4State existing for.
Experimental example 2
The specific surface area and aperture structure of sample are analyzed
The present embodiment sample used is made by Examples 1 to 7.
N is carried out to above-mentioned sample2Adsorption/desorption test, wherein
Fig. 6 shows the N of sample made from embodiment 12Adsorption/desorption (a) and pore size distribution curve figure (b)；
Fig. 7 shows the N of sample made from embodiment 22Adsorption/desorption (a) and pore size distribution curve figure (b)；
Fig. 8 shows the N of sample made from embodiment 32Adsorption/desorption (a) and pore size distribution curve figure (b)；
Fig. 9 shows the N of sample made from embodiment 42Adsorption/desorption (a) and pore size distribution curve figure (b)；
Figure 10 shows the N of sample made from embodiment 52Adsorption/desorption (a) and pore size distribution curve figure (b)；
Figure 11 shows the N of sample made from embodiment 62Adsorption/desorption (a) and pore size distribution curve figure (b)；
Figure 12 shows the N of sample made from embodiment 72Adsorption/desorption (a) and pore size distribution curve figure (b)；
Table 1 shows specific surface area, pore volume and the pore width of sample made from Examples 1 to 7；
Table 1
It is found that sample made from Examples 1 to 7 all shows the allusion quotation of a mesoporous capillary condensation structure from Fig. 6~12
Type IV thermoisopleth, and relative pressure P/P0H3 type hysteresis loop is showed when between 0.45-0.8；
Table 1 gives the specific surface area that all samples are calculated using Brunauer-Emmet-Teller (BET) method,
As the temperature rises, specific surface area is gradually reduced the specific surface area of sample made from embodiment 2~7 instead, this is because Fe
(Fe caused by the crystal transition of species3C → Fe),
And the specific surface area of sample made from embodiment 1 is maximum, is 126.04m2/ g, due to its unspoiled structure and
High porosity makes it that higher adsorption capacity be presented for other samples.
Experimental example 3
The thermogravimetric analysis of sample
The present embodiment sample used is made by Examples 1 to 7.
In air atmosphere to above-mentioned sample, with 10min-1Rate 1000 DEG C of progress thermogravimetric analysis are heated to from 30 DEG C,
Wherein,
Figure 13 shows the thermogravimetric curve (respectively corresponding curve a~g) of sample made from Examples 1 to 7；
As shown in Figure 13, in the burning and decomposition that temperature is between 400 DEG C -650 DEG C due to carbon or carbide, embodiment
Sample quality made from 2~6 has lost about 5%, 16%, 18%, 28% and 24% respectively, these mass losses mainly due to
The release of carbon nitride gas, such as C2N2 +, C3N3 +Deng；
On the contrary, embodiment 1 and embodiment 7 have the tendency that a quality rises in temperature between 400 DEG C -450 DEG C,
This is because caused by the oxidation of nano zero valence iron,
And sample made from embodiment 7 first increases the trend reduced afterwards in 400 DEG C of -650 DEG C of appearance, this may be due to this
The amount of the nano zero valence iron contained in sample is more caused for the sample made from the embodiment 2~6.
The thermogravimetric curve of sample made from Examples 1 to 7 is all stable after 650 DEG C, illustrates during mass loss
A small amount of variation only occurs, and remaining substance is the oxide and carbide of iron.
Experimental example 4
Removing to Luo Ming pellet B (RhB) for sample is studied
The present embodiment sample used is made by Examples 1 to 7.
Experiment of the above-mentioned sample to the removal effect of RhB is carried out, it is as shown in figure 14 to obtain result, wherein
Figure 14 shows sample made from Examples 1 to 7 to the removal efficiency (respectively corresponding curve a~g) of RhB；
As shown in Figure 14, sample (Fe/Fe made from embodiment 13O4/ PGC) to the removal rate highest of RhB, reach
94.1%, it is not bound by any theory, it has been recognised by the inventors that this is because nano zero valence iron (nZVI) partial size is small, high surface activity
Chemistry and architectural characteristic, and be dispersed on graphitized carbon well, to improve the contact area and reaction site of nZVI,
Promote the removal to RhB, simultaneously because Fe/Fe3O4/ PGC specific surface area with higher and hole for other materials
Volume makes it have stronger adsorption capacity.
And sample made from embodiment 7 has slightly higher removal energy for the sample made from the embodiment 2~6
Power, this may be due to caused by its relatively high crystallinity and higher nZVI content.
Experimental example 5
The stability study of sample
The present embodiment sample used is made by embodiment 1.
Measure the XRD spectra after testing and after placing 15 days in air respectively above-mentioned sample removal RhB mono- and four times
And scanning electron microscope (SEM) photograph, it is as shown in Figure 15 and Figure 16 to obtain result, wherein
Figure 15 shows (curve a), experiment 1 (4 curve b), experiment (curve c) before sample experiments made from embodiment 1
(the XRD diagram of curve d) after placing 15 days in air
Figure 16 shows (a), in air (b) and 4 times (c) of experiment after placement 15 days before sample experiments made from embodiment 1
Scanning electron microscope (SEM) photograph；
As shown in Figure 15, the main substance of sample room (Fe and Fe3O4) there is no significantly changing, iron passing through of species
The mode for learning key is embedded in reactivity and stability that this damascene structures in C framework are conducive to be promoted material itself, passes through
Steric effect weakens the reunion due to caused by nano iron oxide itself magnetism, illustrates that the stability of this sample is fine, even
The preservation of short time is also not easy to be oxidized in air.
As shown in Figure 16, nano zero valence iron is evenly distributed on graphitized carbon skeleton, and particle size is different, illustrates stone
Inkization carbon is the oxidation that a kind of good solid carrier is used to prevent nZVI.Similar whole result and particle diameter distribution can be
(b) discovery in, it can be seen that even if after exposing 15 days in air, since this damascene structures significantly improve material
Stability.
However, sample, after reacting 4 times with RhB (c), the size of nano particle significantly increases, this is because nZVI quilt
Consumption is formed caused by the oxide of iron, and is formed on its surface layer of oxide layer.
The recycling Journal of Sex Research of 6 sample of experimental example
The present embodiment sample used is made by embodiment 1.
Measure respectively above-mentioned sample reuse 1,2,3 and 4 time to RhB in solution removal rate (respectively correspond curve a,
B, c, d), it is as shown in figure 17 to obtain result, wherein
As shown in Figure 17, sample gradually weakens the removal rate of RhB in solution with the increase of access times, from
94.1% drops to 60.1%, but material still can keep removal rate 60% or more after being repeated 3 times, and illustrate with circulation
Nano zero valence iron in the increase composite material of number is gradually consumed, while nano zero valence iron is inevitably by solution
Oxygenated water or the corrosion of other dissolved organic matters make it lose reactivity site in surface formation oxide layer to prevent into one
Walk the removal to RhB.
It can be seen that nano zero valence iron is the most important factor for removing RhB, it is right after nano zero valence iron is depleted
What the removal of RhB was mainly completed by absorption, this result illustrates that again this embedded type structure not only can protect
Material is not easy to be oxidized, and can also improve the reactivity and stability of material itself simultaneously.
Influence of 7 initial pH value of experimental example to sample removal RhB effect
The present embodiment sample used is made by embodiment 1.
Experiment measures, certain sample input amount, after reacting 120min, RhB concentration from 5mg/L, 10mg/L,
When 15mg/L increases to 20mg/L, sample made from embodiment 1 is to RhB removal rate respectively under 99.3%, 98.8%, 97.4%
95.6% is dropped to, and the removal rate of RhB is concentrated mainly on preceding 20-40min, so selecting the RhB of 10mg/L for initial concentration；
Experiment measures, and after reacting 120min, sample dosage increases to 1g/ from 0.25g/L, 0.5g/L, 0.75g/L
When L, sample made from embodiment 1 rises to 99.5% from 54.3%, 94.1%, 99.3% respectively to the removal rate of RhB, due to
Removal rate when dosage is 0.75g/L is close with removal rate when 1g/L, thus our sample dosages for selecting for
0.75g/L；
After reacting 120min, the initial concentration solution of RhB is 10mg/L for measurement, when sample dosage is 0.75g/L,
Influence of the initial pH value to the RhB removal rate of sample, the pH value of solution are respectively adjusted to 3,5,7,9 with HCl and NaOH, as a result such as
Shown in Figure 18, wherein
It is respectively that sample made from 3,5,7,9 pairs of embodiments 1 (respectively corresponds RhB removal rate that Figure 18, which shows initial pH value,
Curve a~d)；
Sample made from embodiment 1 drops to RhB removal rate from 97.37%, 91.62%, 89.89% respectively
86.76%, illustrate that the removal rate of the increase RhB with PH decreases,
It is not bound by any theory, it has been recognised by the inventors that influence of the initial pH value to the removal rate of sample is mainly due to two
A factor, the existence of RhB ion and the surface charge properties of Fe species in solution.RhB existence has 2 kinds of different electricity
The fundamental type of lotus: cationic form (RhB+) and zwitterionic state (RhB±).When pH value is lower than dissociation constant, RhB master
It to be existed in solution with cationic state, on the contrary, working as pH value due to the deprotonation of carboxylic group in RhB molecule
When higher than dissociation constant, RhB is mainly existed in solution with zwitterionic state.Pass through the knot of the Zeta potential of nano zero valence iron
Fruit it is found that its isoelectric point all 7.0 or so or smaller, that is to say, that material surface is positively charged in acid condition, due to
Electrostatic attraction, therefore it is more advantageous to absorption RhB.
In addition, influence of the pH value to the removal rate of RhB is not only by influencing the positive and negative of RhB and adsorbent surface charge
Property, while significant impact can be also generated to oxidation reaction, it reacts as follows:
Fe0+O2+2H+→Fe2+H2O2 (7-1)
Fe2++H2O2→Fe3++OH+OH- (7-2)
Fe0+Fe3+=Fe2+ (7-3)
The kinetics and Adsorption thermodynamics research of 8 sample of experimental example
The present embodiment sample used is made by embodiment 1.
The removal effect of the preceding 20min of removal of the sample to RhB is taken to carry out kinetics and Adsorption thermodynamics respectively
Research,
First by being simulated using quasi- First order dynamic model:
qt=(C0-Ct)×V/M (8-1)
ln(qe-qt)=ln qe-k1t (8-2)
Wherein, t indicates any time (min) that reaction carries out, C0And CtIndicate solution when initial time and any time t
The concentration (mg/L) of middle RhB, V are liquor capacity (m3), M is the quality (g) that adsorbent is added in solution, qt、qeIt respectively represents
Any time and reaction reach the unit adsorbance (mg/g) when balance, k1For secondary absorption kinetic constant (mg/ (g
min))。
Table 2 indicates the quasi- first _ order kinetics equation parameter of sample removal RhB under the conditions of different PH, as shown in Table 2, relatively
It is fitted in second order dynamic model, coefficient R2≤ 0.984 is lower, more meets second-order kinetics rule.
Table 2
Second-order kinetics are investigated again:
Wherein, k2For secondary absorption kinetic constant (mg/ (gmin)), by using t as abscissa, t/qtFor ordinate
It is fitted, it can be in the hope of the q in adsorption process from the slope and intercept of fitting resulteWith t value, the data result band that will be obtained
Enter to calculate, as a result shown in table 3, table 3 shows the quasi- second-order kinetic equation parameter of sample removal RhB under different pH condition,
Table 3
As seen from Table 3, the coefficient R under each pH condition2Value be all larger than 0.9941, that is, adsorption process is
Except the rate-determining step of RhB.In addition, the variation of pH is to k2Cause apparent influence, pH value from 3 rise to 7 during, k2From
0.033 drops to 0.011, further illustrates the importance that pH value removes sample to RhB.
Furthermore in the research of Adsorption thermodynamics,
Freundlich model mainly describes the adsorption equilibrium of multiphase absorption surface, and equation is as follows:
Langmuir model mainly describes the monolayer adsorption occurred on a uniform outer surface, and between adsorbate
It does not react, equation is as follows:
Wherein, Ce, qeRespectively indicate the equilibrium concentration and unit adsorbance (mg/g) of RhB when reaction reaches balance, Q0It indicates
Maximal absorptive capacity Qmax(mg/g), kFIt is constant with n, respectively indicates adsorption capacity and adsorption strength, pass through C respectivelyeAnd lnCeFor
Abscissa, with Ce/qeAnd lnqeIt is fitted for ordinate, it can be in the hope of experimental data knot from the slope and intercept of fitting result
Fruit, table 4 show Freundlich the and Langmuir thermoisopleth parameter of sample removal RhB,
Table 4
| Isotherm model | KF(mg1-1/n L1/n/g) | 1/n | qm(mg/g) | KL(L/mg) | R2 |
| Freundlich | 18.14 | 0.149 | - | - | 0.796 |
| Langmuir | - | - | 22.22 | 15.01 | 0.999 |
As shown in Table 4, RhB occurs in Fe/Fe3O4The monolayer adsorption of the uniform surface binding site of/PGC, maximal absorptive capacity
For 22.22mg/g, there is very high adsorption capacity.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (10)
1. a kind of composite material of load iron, which is characterized in that
The composite material has iron using carbon material as carrier, in supported on carriers.
2. composite material according to claim 1, which is characterized in that
The carbon material is active carbon or graphitized carbon, preferably graphitized carbon (PGC), it is preferable that provides the carbon material
Carbon source is organic carbon source, preferably carboritride, more preferably one of melamine, dicyanodiamine, urea, cyanamide
Or a variety of, especially preferably melamine.
3. composite material according to claim 1, which is characterized in that
The iron is selected from one or more of iron simple substance and the compound of iron,
The iron simple substance is Zero-valent Iron, preferably nano-level iron,
The compound of the iron is the oxide of iron or the carbide of iron, the preferably oxide of iron,
It is highly preferred that the mode of the carbon material supported iron be it is embedded, the mode that preferably chemical bond is crossed by Tie Tong is embedded in carbon skeleton
In.
4. composite material according to claim 1, which is characterized in that
The specific surface area of the composite material is 50m2/ g~130m2/ g, pore volume 0.05cm3/ g~0.3cm3/ g, porosity
For 4nm~10nm.
5. a kind of method for the composite material for preparing load iron described in one of Claims 1 to 4, the method includes following steps
It is rapid:
Step (1) mixes carbon source and source of iron；
Step (2), the mixture that step (1) is obtained are calcined, and the composite material of load iron is obtained.
6. according to the method described in claim 5, it is characterized in that,
In step (1), the carbon source is organic carbon source, preferably carboritride, more preferably melamine, dicyanodiamine,
One of urea, cyanamide are a variety of, especially preferably melamine,
The source of iron is molysite or ferrous salt, preferably molysite, more preferably iron chloride, ferric nitrate, ferric sulfate, in ferric acetate
One kind, especially preferably iron chloride.
The molar ratio of the carbon source and source of iron is 5~10:1, preferably 6~9:1, more preferably 8:1.
7. according to the method described in claim 5, it is characterized in that,
In step (1), mixed carbon source and source of iron are stirred at 50 DEG C~100 DEG C, preferably stirred at 60 DEG C~90 DEG C, more
It is preferred that being stirred at 80 DEG C.
In step (2), the calcining carries out under the atmosphere for being passed through inert gas, preferably starts to be passed through indifferent gas before being calcined
Body,
The flow of inert gas is 30mL/min~70mL/min, preferably 40mL/min~60mL/min, more preferably 50mL/
min。
8. according to the method described in claim 5, it is characterized in that,
In step (2), the temperature of the calcining is 680 DEG C~1000 DEG C, preferably 700 DEG C~900 DEG C, more preferably 700 DEG C,
And/or
Calcination temperature is warming up to by certain heating rate, the heating rate is 3 DEG C/min~10 DEG C/min, preferably 4 DEG C/
Min~8 DEG C/min, more preferably 5 DEG C/min, and/or
1h~4h, preferably 1.5h~3h, more preferable 2h are kept the temperature at calcination temperatures.
9. the method according to one of claim 5 to 8, which is characterized in that
In step (2), the composite material of obtained load iron has iron, preferably Tie Tong using carbon material as carrier, in supported on carriers
The mode for crossing chemical bond is embedded in carbon skeleton,
It is to be respectively present crystallographic plane diffraction peak at 44.7 ° and 65.1 ° in 2 θ of the angle of diffraction according to its XRD analysis.
10. according to claim 1 to the composite material of load iron described in one of 4 or according to one of claim 5 to 9
Application in terms of the application of the composite material of the load iron of method preparation, especially processing organic dyestuff sewage.
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