CN103752313A - Fe-supported mesoporous carbon material, and preparation method and application thereof - Google Patents
Fe-supported mesoporous carbon material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a Fe-supported mesoporous carbon material. The method comprises the following steps of supporting dicyclopentadienyl iron in a pore passage of a porous template material by using a physical vapor deposition method, performing high-temperature carbonization, and removing the porous template material to obtain the Fe-supported mesoporous carbon material. According to the preparation method, the dicyclopentadienyl iron serves as a carbon source and an iron source simultaneously, and the Fe-supported mesoporous carbon material can be prepared by one step without secondary preparation; the Fe-supported mesoporous carbon material obtained by the method has the characteristics of mesoporous pore passage, large specific surface area and uniform aperture distribution; moreover, Fe is uniformly distributed in a substrate of the mesoporous carbon material without agglomeration phenomena, and the Fe-supported mesoporous carbon material can serve as an out-of-phase Fenton reaction catalyst, an adsorbent, a fischer-tropsch synthesis catalyst, other catalytic oxidizers and the like.
Description
Technical field
The present invention relates to a kind of meso-porous carbon material, relate in particular to meso-porous carbon material of a kind of load Fe as heterogeneous Fenton catalyst and its preparation method and application.
Background technology
Advanced oxidation processes (AOP) is to process the effective method of one being difficult in water with bioanalysis or common physical-chemical process (filtering sedimentation) pollutant that remove and that have bio-toxicity.It is usually used in the pretreatment to water pollutant, and biological treatment and common physical-chemical process are had place to show one's prowess.In AOP method, conventional oxidant has ozone, hydrogen peroxide, oxygen, and is aided with effective catalyst.Fenton system (Fe
n+with H
2o
2) process organic pollution owing to can not producing poisonous accessory substance and reaction condition gentleness has caused people's attention.The Main Function of Fenton system is to produce electrophilic strong oxidizer hydroxyl radical free radical (HO), it can be fast and the high polymer of the attack electron rich of non-selectivity, makes high polymer be degraded to stable inorganic compound as water, carbon dioxide, salt etc. and mineralization occurs; Or with the polymer degradation of bioanalysis degraded, be biodegradable material by difficulty.
Fenton reaction system can be write as following form: Fe
n++ H
2o
2→ M
(n-1)++ OH
-+ HO.But homogeneous phase Fenton reacts in use due to existence: (1) H
2o
2consumption is many, and cost is high; (2) pH value scope is too narrow, needs to consume a large amount of acid to maintain pH value; (3) Fe is difficult reclaims, and in water, Fe content is high, does not meet corresponding environmental regulations; (4) need to carry out the problems such as post processing and hinder it and used on a large scale.Heterogeneous Fenton catalyst arises at the historic moment, and it is that active specy Fe is loaded on solid carrier, as upper in zeolite, mesoporous material, clay, activated carbon, resin, Al base material etc., the problem existing to improve homogeneous phase Fenton system.
Meso-porous carbon material is because its high specific area has splendid absorption property, is beneficial to the carrying out of Fenton reaction and caused people's concern.Meso-porous carbon material often adopts hard template method, soft template method and wet dipping to prepare.Hard template method is carbon source to be filled in the duct of the foraminous die plates such as SBA-15, KIT-6, MCM-41 or zeolite, the meso-porous carbon material that has copied mould material shape after high temperature carbonization, mould material removal being obtained.The meso-porous carbon material that this method is prepared is because high-sequential is widely studied.Soft template method is to utilize microemulsion that surfactant forms as template, utilizes resin etc. to make after charing for carbon source.Although soft template method can regulate and control aperture and the specific surface area size of meso-porous carbon material, preparation process difficult control of reaction conditions, needs the reaction condition of regulation and control more.Wet infusion process is to prepare the common method of supported active metal meso-porous carbon material, but due to capillary impact in preparation process, active metal is assembled, thereby specific area, aperture and the pore volume of meso-porous carbon material have been reduced, even stop up the duct of meso-porous carbon material, thereby reduced the transportation of material in inside, duct, reduced catalytic efficiency.And in the meso-porous carbon material that obtains of wet infusion process a little less than the active force between active metal and matrix, make the easy loss of active metal further reduce its catalytic activity.Therefore can prepare the equally distributed meso-porous carbon material of a kind of active metal in the urgent need to.
In Fenton reaction, Fe
2+with H
2o
2reaction rate higher than Fe
3+with H
2o
2reaction rate, therefore Fe
2+the height of content and be easy to regenerate Fe
2+ability determined the reaction rate of heterogeneous Fenton.Meanwhile, most of heterogeneous Fenton catalyst only has catalytic activity under acid condition (pH=3), has hindered the practical application of these materials.Therefore, prepare a kind of Fe
2+the heterogeneous Fenton catalyst that content is high, catalytic activity is high, Fe number of dropouts is low, can use under neutrallty condition also in the urgent need to.
Summary of the invention
The present invention is directed to Metal Distribution in the meso-porous carbon material of prior art supported active metal inhomogeneous, in heterogeneous Fenton catalyst, low, the Fe of Fe content runs off seriously and only under acid condition, just has the technical problem of catalytic activity, and meso-porous carbon material providing a kind of new load Fe and its preparation method and application is provided object.
The method of the meso-porous carbon material of preparation load Fe of the present invention comprises the steps: A) adopt physical vaporous deposition that ferrocene is loaded in the duct of foraminous die plate material, obtain the foraminous die plate material of load ferrocene; B) by the foraminous die plate material of load ferrocene through high temperature carbonization and remove foraminous die plate material, obtain the meso-porous carbon material of load Fe.In preparation method of the present invention by ferrocene simultaneously as carbon source and source of iron, without secondary preparation, can a step obtain the meso-porous carbon material of load Fe.
Steps A) described in physical vaporous deposition be at 110 ℃～200 ℃ preferred 110 ℃ of deposition 5h～80h preferred 48h, obtain the foraminous die plate material of load ferrocene.
Step B) specifically by the foraminous die plate material of load ferrocene under non-oxygen atmosphere through 400 ℃～600 ℃ preferably 450 ℃ of high temperature cabonizations process the preferred 1h of 1h～5h; Then in 60 ℃～100 ℃, preferably in the strong base solution of 80 ℃, process the preferred 2h of 0.5h～5h to remove foraminous die plate material, filter and be dried the meso-porous carbon material that obtains load Fe.Described highly basic refers to NaOH, KOH or the LiOH solution of 2M～5M, described dry referring at 40～100 ℃ of preferred 70 ℃ of dry 6～24h.Described non-oxygen atmosphere refers to hydrogen, nitrogen, ammonia, helium or argon gas atmosphere.
Described foraminous die plate material can be foraminous die plate material arbitrarily, for example, be the mesoporous silicon based material of KIT-6, SBA-15, MCM-48, HMS or MSU-H, or be, AAO or zeolite.
The present invention also provides the meso-porous carbon material of the load Fe that a kind of method of the present invention prepares.The specific area of the meso-porous carbon material of this load Fe is 650～700m
2/ g, pore volume are 0.35～0.45cm
3/ g, average pore size 3～4nm, Fe
2+content higher than 35%, preferably Fe
2+content be 35%～56%.The Fe content of the meso-porous carbon material of the load Fe that method of the present invention obtains is higher than the meso-porous carbon material preparing by infusion process, and there is no the generation of agglomeration; It has, and meso-porous nano duct, specific area are large, the feature of even aperture distribution, and Fe is evenly distributed in the matrix of meso-porous carbon material.
The meso-porous carbon material of load Fe of the present invention is in the application as in heterogeneous Fenton catalyst, adsorbent, fischer-tropsch synthetic catalyst or other catalytic oxidant.When the meso-porous carbon material of described load Fe is used as heterogeneous Fenton catalyst, there is higher activity, with 200mg.L
-1methylene blue solution be example, can realize under neutrallty condition in 150min its 100% degraded, and almost there is no Fe run off (< 0.003ppm).
Accompanying drawing explanation
Figure 1A is the XRD collection of illustrative plates that embodiment 1 makes meso-porous carbon material;
Figure 1B is nitrogen adsorption desorption isothermal curve and the graph of pore diameter distribution that embodiment 1 makes meso-porous carbon material;
Fig. 1 C is the TEM figure that embodiment 1 makes meso-porous carbon material;
Fig. 1 D is the EDX energy spectrogram that embodiment 1 makes meso-porous carbon material;
Fig. 2 A is the XRD collection of illustrative plates that embodiment 2 makes meso-porous carbon material;
Fig. 2 B is nitrogen adsorption desorption isothermal curve and the graph of pore diameter distribution that embodiment 2 makes meso-porous carbon material;
Fig. 2 C is the TEM figure that embodiment 2 makes meso-porous carbon material;
Fig. 2 D is the EDX energy spectrogram that embodiment 2 makes meso-porous carbon material;
Fig. 3 A is the XRD collection of illustrative plates that embodiment 3 makes meso-porous carbon material;
Fig. 3 B is nitrogen adsorption desorption isothermal curve and the graph of pore diameter distribution that embodiment 3 makes meso-porous carbon material;
Fig. 4 A is the XRD collection of illustrative plates that embodiment 4 makes meso-porous carbon material;
Fig. 4 B is nitrogen adsorption desorption isothermal curve and the graph of pore diameter distribution that embodiment 4 makes meso-porous carbon material;
Fig. 5 A is the XRD collection of illustrative plates that embodiment 5 makes meso-porous carbon material;
Fig. 5 B is nitrogen adsorption desorption isothermal curve and the graph of pore diameter distribution that embodiment 5 makes meso-porous carbon material;
Fig. 6 A is the XRD collection of illustrative plates that embodiment 6 makes meso-porous carbon material;
Fig. 6 B is nitrogen adsorption desorption isothermal curve and the graph of pore diameter distribution that embodiment 6 makes meso-porous carbon material;
Fig. 7 A is the XRD collection of illustrative plates that embodiment 7 makes meso-porous carbon material;
Fig. 7 B is nitrogen adsorption desorption isothermal curve and the graph of pore diameter distribution that embodiment 7 makes meso-porous carbon material;
Fig. 8 A is the XRD collection of illustrative plates that embodiment 8 makes meso-porous carbon material;
Fig. 8 B is nitrogen adsorption desorption isothermal curve and the graph of pore diameter distribution that embodiment 8 makes meso-porous carbon material;
Fig. 9 A is the Xps collection of illustrative plates of the Fe2p of the meso-porous carbon material that makes of embodiment 1;
Fig. 9 B is the Xps collection of illustrative plates of the Fe2p of the meso-porous carbon material that makes of embodiment 2;
Figure 10 A is the absorbance collection of illustrative plates over time of the meso-porous carbon material degradation of methylene blue of embodiment 1;
Figure 10 B is the absorbance collection of illustrative plates over time of the meso-porous carbon material degradation of methylene blue of embodiment 2.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.But, should be understood that these embodiment only do not form limitation of the scope of the invention for the present invention is described.The test method of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.
Prepare foraminous die plate material (take mesoporous silicon material KIT-6 as example)
First by 4.0g P123(PEO-PPOX-PEO triblock copolymer) and the HCl of 7.9g35wt% be dissolved in 144g water, at 35 ℃, be stirred to dissolving.Subsequently 4.0g n-butanol is added drop-wise in above-mentioned solution fast, continues to stir 1h.Again 8.6g ethyl orthosilicate is added drop-wise in above-mentioned settled solution, stirs 24h.And then be placed in the baking oven hydrothermal treatment consists 24h of 100 ℃.After filtration, dry 24h in the baking oven of 100 ℃, then be placed in Muffle furnace and be warmed up to after 550 ℃ and be incubated 6h with the speed of 1 ℃/min, obtain KIT-6 foraminous die plate material.
Embodiment 1
KIT-6 and ferrocene put into respectively to crucible and be placed in airtight wide-mouth bottle simultaneously, at 110 ℃, process 48h, obtaining the KIT-6 of load ferrocene.The KIT-6 of load ferrocene is warmed up under nitrogen atmosphere to 450 ℃ and be incubated 1h; Then in the 2M NaOH of 80 ℃, process 2h to remove foraminous die plate material KIT-6, filter and obtain at 70 ℃ of dry 12h the meso-porous carbon material of load Fe.Meso-hole structure parameter is as shown in table 1.
From Figure 1A, this meso-porous carbon material is amorphous state; Figure 1B is visible, thermoisopleth be typical IV type with H1 type hysteresis loop, be typical meso-hole structure, and its pore-size distribution homogeneous; Fig. 1 C and Fig. 1 D are visible, and the meso-hole structure of meso-porous carbon material is apparent, and even aperture distribution, and Fe is distributed in the matrix of meso-porous carbon material, but there is no the generation of agglomeration.
KIT-6 and ferrocene are put into respectively to crucible and be placed in airtight wide-mouth bottle simultaneously, at 110 ℃, process the KIT-6 of 48h acquisition load ferrocene.The KIT-6 of load ferrocene is warmed up under hydrogen atmosphere to 450 ℃ and be incubated 1h; Then in the 2M NaOH of 80 ℃, process 2h to remove foraminous die plate material KIT-6, filter and obtain in 70 ℃ of dry 12h the meso-porous carbon material of load Fe.Its meso-hole structure parameter is as shown in table 1.
From Fig. 2 A, meso-porous carbon material is amorphous state; From Fig. 2 B, thermoisopleth be typical IV type with H1 type hysteresis loop, be typical meso-hole structure, and its pore-size distribution homogeneous; From Fig. 2 C and Fig. 2 D, the meso-hole structure of meso-porous carbon material is apparent, and even aperture distribution, and Fe is distributed in the matrix of meso-porous carbon material, but there is no the generation of agglomeration.
Embodiment 3
KIT-6 and ferrocene are put into respectively to crucible and be placed in airtight wide-mouth bottle simultaneously, at 110 ℃, process the KIT-6 of 5h acquisition load ferrocene.The KIT-6 of load ferrocene is warmed up under hydrogen atmosphere to 450 ℃ and be incubated 1h; Then in the 5M NaOH of 100 ℃, process 0.5h to remove foraminous die plate material KIT-6, filter and obtain in 40 ℃ of dry 24h the meso-porous carbon material of load Fe.Its meso-hole structure parameter is as shown in table 1.
From Fig. 3 A, meso-porous carbon material is amorphous state; From Fig. 3 B, thermoisopleth be typical IV type with H1 type hysteresis loop, be typical meso-hole structure, and its pore-size distribution homogeneous.
KIT-6 and ferrocene are put into respectively to crucible and be placed in airtight wide-mouth bottle simultaneously, at 110 ℃, process the KIT-6 of 80h acquisition load ferrocene.The KIT-6 of load ferrocene is warmed up under hydrogen atmosphere to 450 ℃ and be incubated 2h; Then in the 2M NaOH of 60 ℃, process 5h to remove foraminous die plate material KIT-6, filter and obtain in 100 ℃ of dry 6h the meso-porous carbon material of load Fe.Its meso-hole structure parameter is as shown in table 1.
From Fig. 4 A, meso-porous carbon material is amorphous state; From Fig. 4 B, thermoisopleth be typical IV type with H1 type hysteresis loop, be typical meso-hole structure, and its pore-size distribution homogeneous.
KIT-6 and ferrocene are put into respectively to crucible and be placed in airtight wide-mouth bottle simultaneously, at 110 ℃, process the KIT-6 of 65h acquisition load ferrocene.The KIT-6 of load ferrocene is warmed up under hydrogen atmosphere to 400 ℃ and be incubated 5h; Then in the 2M NaOH of 100 ℃, process 1.5h to remove foraminous die plate material KIT-6, filter and obtain in 70 ℃ of dry 12h the meso-porous carbon material of load Fe.Its meso-hole structure parameter is as shown in table 1.
From Fig. 5 A, meso-porous carbon material is amorphous state; From Fig. 5 B, thermoisopleth be typical IV type with H1 type hysteresis loop, be typical meso-hole structure, and its pore-size distribution homogeneous.
KIT-6 and ferrocene are put into respectively to crucible and be placed in airtight wide-mouth bottle simultaneously, at 200 ℃, process the KIT-6 of 10h acquisition load ferrocene.The KIT-6 of load ferrocene is warmed up under hydrogen atmosphere to 500 ℃ and be incubated 1h; Then in the 3M NaOH of 60 ℃, process 1.5h to remove foraminous die plate material KIT-6, filter and obtain in 80 ℃ of dry 10h the meso-porous carbon material of load Fe.Its meso-hole structure parameter is as shown in table 1.
From Fig. 6 A, meso-porous carbon material is amorphous state; From Fig. 6 B, thermoisopleth be typical IV type with H1 type hysteresis loop, be typical meso-hole structure, and its pore-size distribution homogeneous.
Embodiment 7
KIT-6 and ferrocene are put into respectively to crucible and be placed in airtight wide-mouth bottle simultaneously, at 110 ℃, process the KIT-6 of 48h acquisition load ferrocene.The KIT-6 of load ferrocene is warmed up under hydrogen atmosphere to 600 ℃ and be incubated 1h; Then in the 2M NaOH of 80 ℃, process 2h to remove foraminous die plate material KIT-6, filter and obtain in 70 ℃ of dry 12h the meso-porous carbon material of load Fe.Its meso-hole structure parameter is as shown in table 1.
From Fig. 7 A, meso-porous carbon material is amorphous state; From Fig. 7 B, thermoisopleth be typical IV type with H1 type hysteresis loop, be typical meso-hole structure, and its pore-size distribution homogeneous.
SBA-15 and ferrocene are put into respectively to crucible and be placed in airtight wide-mouth bottle simultaneously, at 110 ℃, process the SBA-15 of 17h acquisition load ferrocene.The SBA-15 of load ferrocene is warmed up under nitrogen atmosphere to 450 ℃ and be incubated 1h; Then in the 2M NaOH of 80 ℃, process 2h to remove foraminous die plate material KIT-6, filter and obtain in 70 ℃ of dry 12h the meso-porous carbon material of load Fe.Its meso-hole structure parameter is as shown in table 1.
From Fig. 8 A, meso-porous carbon material is amorphous state; From Fig. 8 B, thermoisopleth be typical IV type with H1 type hysteresis loop, be typical meso-hole structure, and its pore-size distribution homogeneous.
The mesoporous parameter of the meso-porous carbon material of table 1 embodiment 1～8
From Fig. 9 A, the Fe2p of the meso-porous carbon material of embodiment 1 can be divided into two peaks, and 711eV and 713eV correspond respectively to Fe
2+and Fe
3+, its content is 56.78% and 43.22%, has higher Fe
2+content.From Fig. 9 B, the Fe2p of the meso-porous carbon material of embodiment 2 can be divided into three peaks, and 710eV, 711eV and 713eV correspond respectively to Fe
0, Fe
2+and Fe
3+, its content is respectively 49.08%, 35.76% and 15.16%, Fe
0existence can be by Fe
3+be reduced to Fe
2+thereby, improve its heterogeneous Fenton speed.
Effect embodiment
Measure two parts of 25mL200mg.L
-1methylene blue solution, take respectively 0.6g.L
-1the meso-porous carbon material of embodiment 1 and embodiment 2 is in the above-mentioned solution of adjusting without pH value, and lucifuge, to prevent the impact of light on reaction, stirs 3h to reaching adsorption equilibrium at 30 ℃.By the H of 150mM30wt%
2o
2be added drop-wise in the above-mentioned solution that reaches balance to start Fenton reaction, every reaction 30min extracts 3mL solution with disposable syringe, via hole diameter is to get supernatant after the disposable syringe filter of 0.45um filters, and carries out the detection of dye strength with ultraviolet-uisible spectrophotometer after diluting 3 times.
From Figure 10 A, the meso-porous carbon material of embodiment 1 can be realized the degraded of 98% methylene blue solution in 150min; From Figure 10 B, the meso-porous carbon material of embodiment 2 can be realized whole degradeds of methylene blue solution in 150min.
Claims (10)
1. prepare a method for the meso-porous carbon material of load Fe, it is characterized in that the method comprises the steps: A) adopt physical vaporous deposition that ferrocene is loaded in the duct of foraminous die plate material, obtain the foraminous die plate material of load ferrocene; B) by the foraminous die plate material of load ferrocene through high temperature carbonization and remove foraminous die plate material, obtain the meso-porous carbon material of load Fe.
2. the method for claim 1, is characterized in that: steps A) described in physical vaporous deposition be at 110 ℃～200 ℃ preferred 110 ℃ of deposition 5h～80h preferred 48h, obtain the foraminous die plate material of load ferrocene.
3. the method for claim 1, is characterized in that: step B) specifically by the foraminous die plate material of load ferrocene under non-oxygen atmosphere through 400 ℃～600 ℃ preferably 450 ℃ of high temperature cabonizations process the preferred 1h of 1h～5h; Then in 60 ℃～100 ℃, preferably in the strong base solution of 80 ℃, process the preferred 2h of 0.5h～5h to remove foraminous die plate material, filter and be dried the meso-porous carbon material that obtains load Fe.
4. method as claimed in claim 3, is characterized in that: described highly basic refers to the NaOH of 2M～5M, KOH or LiOH solution, described dry referring at 40～100 ℃ of preferred 70 ℃ of dry 6～24h.
5. method as claimed in claim 3, is characterized in that: described non-oxygen atmosphere refers to hydrogen, nitrogen, ammonia, helium or argon gas atmosphere.
6. the method for claim 1, is characterized in that: described foraminous die plate material is the mesoporous silicon based material of KIT-6, SBA-15, MCM-48, HMS or MSU-H, or is, AAO or zeolite.
7. the meso-porous carbon material of the load Fe that method claimed in claim 1 obtains.
8. the meso-porous carbon material of load Fe as claimed in claim 7, is characterized in that: the specific area of the meso-porous carbon material of this load Fe is 250～700m
2/ g, pore volume are 0.10～0.75cm
3/ g, average pore size 3～8.5nm, Fe
2+content higher than 35%.
9. the meso-porous carbon material of load Fe as claimed in claim 8, is characterized in that: Fe
2+content be 35%～56%.
10. the meso-porous carbon material of load Fe claimed in claim 7 is in the application as in heterogeneous Fenton catalyst, adsorbent or fischer-tropsch synthetic catalyst.
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| CN109133001A (en) * | 2018-08-23 | 2019-01-04 | 杭州氢源素生物科技有限公司 | A kind of metal powder and souring activity charcoal composite hydrogen manufacturing material |
| CN109166682A (en) * | 2018-08-30 | 2019-01-08 | 深圳大学 | A kind of magnetic porous carbon material and preparation method thereof |
| CN109166682B (en) * | 2018-08-30 | 2020-04-28 | 深圳大学 | Magnetic porous carbon material and preparation method thereof |
| CN109402663A (en) * | 2018-09-04 | 2019-03-01 | 青岛科技大学 | A kind of preparation and its electrolysis aquatic products hydrogen application of the FePx with 3D meso-hole structure |
| CN109402663B (en) * | 2018-09-04 | 2021-09-07 | 青岛科技大学 | Preparation of FePx with 3D mesoporous structure and application of FePx in hydrogen production by electrolyzing water |
| CN110292927A (en) * | 2019-04-30 | 2019-10-01 | 北京氦舶科技有限责任公司 | Monoatomic metal catalyst and its preparation and the application in degradation air pollutants |
| CN115722273A (en) * | 2022-10-23 | 2023-03-03 | 河南师范大学 | Method for rapidly preparing iron-carbon composite film catalytic material under assistance of laser |
| CN115722273B (en) * | 2022-10-23 | 2023-10-10 | 河南师范大学 | Method for rapidly preparing iron-carbon composite film catalytic material with assistance of laser |
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