CN103553060A - Synthetic method of iron oxide/zero-valent iron-carrying short-pore mesoporous silica - Google Patents
Synthetic method of iron oxide/zero-valent iron-carrying short-pore mesoporous silica Download PDFInfo
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- CN103553060A CN103553060A CN201310478292.5A CN201310478292A CN103553060A CN 103553060 A CN103553060 A CN 103553060A CN 201310478292 A CN201310478292 A CN 201310478292A CN 103553060 A CN103553060 A CN 103553060A
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- iron oxide
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000010189 synthetic method Methods 0.000 title claims description 7
- 239000011148 porous material Substances 0.000 title abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title description 5
- 239000000377 silicon dioxide Substances 0.000 title description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims 4
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 claims 2
- 238000001308 synthesis method Methods 0.000 claims 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- 150000002505 iron Chemical class 0.000 abstract 3
- 229920001400 block copolymer Polymers 0.000 abstract 2
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 150000004819 silanols Chemical class 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明公开了一种新型的合成载氧化铁/零价铁短孔道介孔硅的方法。它是在常温下将铁盐磨入未去除嵌段共聚物的短孔道介孔硅中，氮气气氛下高温煅烧后得到该材料。嵌段共聚物在合成过程中起着两方面的作用：一方面，它作为模板与硅孔壁形成密闭空间使得大量活性硅羟基能和铁盐形成氢键，让铁盐很好地附着在孔壁内；另一方面，它高温碳化后可部分还原氧化铁形成氧化铁/零价铁不同铁状态的负载。该法与传统的水热合成、浸渍负载相比，方法新颖独特，且能够调控载入氧化铁与零价铁的状态，在芬顿、类芬顿等水处理上有较高的应用价值。
The invention discloses a novel method for synthesizing short-channel mesoporous silicon loaded with iron oxide/zero-valent iron. It is obtained by grinding iron salt into short-channel mesoporous silicon without removing block copolymer at normal temperature, and calcining at high temperature under nitrogen atmosphere. The block copolymer plays two roles in the synthesis process: on the one hand, it acts as a template to form a closed space with the silicon pore wall, so that a large number of active silanols can form hydrogen bonds with the iron salt, so that the iron salt can be well attached to the pore In the wall; on the other hand, it can partially reduce iron oxide after high-temperature carbonization to form the load of different iron states of iron oxide/zero-valent iron. Compared with the traditional hydrothermal synthesis and impregnation loading, this method is novel and unique, and can control the state of loaded iron oxide and zero-valent iron. It has high application value in Fenton and Fenton-like water treatment.
Description
Technical field
The present invention relates to a kind of preparation of mesoporous silicon, particularly the synthetic method of the short duct of a kind of iron oxide bearing/Zero-valent Iron mesoporous silicon.
Background technology
Mesopore silicon oxide, because of its large specific surface, orderly mesoporous pore size and pore size distribution, has broad application prospects in catalysis, separation, biology and field of nanometer material technology.In catalytic applications, although it has good physicochemical property and constructional feature, because it is pure silica material, there is no catalytic activity, need just tool catalytic activity of load active component.Ferric oxide/Zero-valent Iron, as a kind of nano material, has very high catalytic activity at aspects such as processing organic waste water, is desirable active ingredient.Preparation is at present carried iron mesoporous silicon and is mainly contained three kinds of methods: (1) hydrothermal synthesis method: Li etc. have reported this synthetic method, it adopts template, silicon source (TEOS etc.) and source of iron (iron nitrate or iron(ic) chloride etc.), under certain pH, mesoporous silicon [Li Ying through the synthetic iron content of one step hydro thermal method, Feng Zhaochi, Lian Yuxiang, et al. Direct Synthesis of Highly Ordered Fe-SBA-15 Mesoporous Materials Under Weak Acidic Conditions.
microporous Mesoporous Mater. 84 (2005) 41～49].Though this method is simple, need under acidic conditions, carry out, waste water easily impacts environment, can only obtain ferric oxide simultaneously and can not get the state of Zero-valent Iron; (2) dipping or ion exchange method: the method with dipping or ion-exchange in mesoporous silicon is introduced iron active centre, then calcining obtains carrying iron silicon.Lim H etc. adopt this legal system for year iron mesoporous silicon [Lim H, Lee J, Jin S, et al. Highly Active Heterogeneous Fenton Catalyst Using Iron Oxide Nanoparticles Immobilized in Alumina Coated Mesoporous Silica.
chem Commun. (2006) 463～465], this method complicated operation, difficulty is large, and iron may be blocked duct and cause catalytic efficiency reduction; (3) grafting: Li Liang etc. are by adding the organic complex of iron, introduce iron active centre, in mesoporous silicon, carry out functional organic reaction, synthetic iron mesoporous silicon [the Li Liang that carries, Shi Jianlin, Yan Jina, et al. Mesoporous SBA-15 Material Functionalized with Ferrocene Group and Its Use as Heterogeneous Catalyst for Benzene Hydroxylation.
app Catal A. 263 (2004) 213～217].The organic complex of iron has iron porphyrin, ferrocene, silicon ferrocenylferrocene etc.This method is used organic complex iron, and cost is high, pollutes large.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of utilizing solid-phase grinding and P123 dual function to prepare the short duct of iron oxide bearing/Zero-valent Iron mesoporous silicon.
The object of the invention is to be achieved through the following technical solutions, the synthetic method of the short duct of a kind of iron oxide bearing/Zero-valent Iron mesoporous silicon, by completing by step below:
(1) prepare the not Zr-Ce-SBA-15 mesoporous silicon of template agent removing (being called for short ZCS) material;
(2) by Fe (NO
3)
39H
2the abundant mixed grinding of ZCS of O and not template agent removing more than half hour, is warming up to 350 ℃ of calcinings under nitrogen atmosphere, and then is warming up to 700 ℃, 800 ℃ or 900 ℃ of calcinings, obtains 3 kinds of ZCS matrix materials that are written into the ferric oxide/Zero-valent Iron of different ratios.
ZCS described in step (1) utilizes triblock copolymer P123, metal precursor salt and the thermal synthesis of tetraethoxy (TEOS) mixing water with the Zr-Ce-SBA-15 mesoporous silicon of template, and wherein said metal precursor salt is ZrOCl
28H
2o and Ce (NO
3)
36H
2the mixing salt of O.
Fe (NO described in step (2)
3)
39H
2o and the not mass ratio of the ZCS of template agent removing are 0.4:1, and described calcination time is 3h, and described temperature rise rate is 1 ℃/min.
The present invention compared with prior art, its remarkable advantage: (1) is simple to operate, and cost is low, and equipment requirements is simple; (2) segmented copolymer P123 not only makes template but also be carbon matrix precursor in method, has simplified the experimental procedure of preparation; (3) under nitrogen atmosphere, differing temps is calcined ferric oxide and the Zero-valent Iron that can obtain different states; (4) ZCS that the carrier that invention is used is short duct, compares with the isometric duct of SBA-15 material, and its mass transfer speed is faster, better effects if.What according to this method, make carries iron ZCS material in catalysis, absorption, and the fields such as Fenton class Fenton oxidation have broad application prospects.
The present invention, under nitrogen atmosphere, be take P123 as template and carbon matrix precursor.Its mechanism that obtains different iron states is: the silicon hydroxyl that P123 itself is rich in can be combined closely in material duct molysite, utilize high temperature by polymer P 123 carbonizations, the ferric oxide reaction that carbon becomes with molysite decomposes obtains Zero-valent Iron, the rising of temperature, and the growing amount of Zero-valent Iron also increases.Reaction process can be represented by following equation:
Fe(NO
3)
3·9H
2O→Fe
2O
3 + NO
x+ H
2O
Fe
2O
3 + C→Fe
0 + CO
2 。
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo (wherein a: embodiment 1, b: embodiment 2, c: embodiment 3) of the short duct of embodiment 1-3 gained iron oxide bearing/Zero-valent Iron mesoporous silicon.
Fig. 2 is X-ray diffraction (XRD) figure (a wherein: each embodiment small-angle diffraction, b: each embodiment wide-angle diffraction) of the short duct of embodiment 1-3 gained iron oxide bearing/Zero-valent Iron mesoporous silicon.
Fig. 3 is the nitrogen adsorption-desorption of embodiment 1,2, the 3 short duct of gained iron oxide bearing/Zero-valent Iron mesoporous silicons and graph of pore diameter distribution (a wherein: each embodiment specific surface figure, b: each embodiment graph of pore diameter distribution).
Embodiment
The first step: by 0.001moLZrOCl
28H
2o and Ce (NO
3)
36H
2the salts solution of O adds in 35 ℃ of aqueous solution containing 2gP123, stirs 0.5h; After forming homogeneous mixed solution, once add 4.5mLTEOS, continue to stir 20h at 35 ℃; By the colloid obtaining 100 ℃ of crystallization 24h in autoclave, use a large amount of deionized water wash after being cooled to room temperature, at 60 ℃, be dried into powder.
Second step: get powder and Fe (NO that mass ratio is 0.4:1
3)
39H
2more than O grinds half hour in mortar, insert in tube furnace after ground, first 350 ℃ of calcining 3h under nitrogen atmosphere, 1 ℃/min to 700 ℃ then, then calcine 3h, can obtain iron oxide bearing ZCS.
The first step: by 0.001moLZrOCl
28H
2o and Ce (NO
3)
36H
2the salts solution of O adds in 35 ℃ of aqueous solution containing 2gP123, stirs 0.5h; After forming homogeneous mixed solution, once add 4.5mLTEOS, continue to stir 20h at 35 ℃; By the colloid obtaining 100 ℃ of crystallization 24h in autoclave, use a large amount of deionized water wash after being cooled to room temperature, at 60 ℃, be dried into powder.
Second step: get powder and Fe (NO that mass ratio is 0.4:1
3)
39H
2more than O grinds half hour in mortar, insert in tube furnace after ground, first 350 ℃ of calcining 3h under nitrogen atmosphere, 1 ℃/min to 800 ℃ then, then calcine 3h, can obtain iron oxide bearing and Zero-valent Iron ZCS.
The first step: by 0.001moLZrOCl
28H
2o and Ce (NO
3)
36H
2the salts solution of O adds in 35 ℃ of aqueous solution containing 2gP123, stirs 0.5h; After forming homogeneous mixed solution, once add 4.5mLTEOS, continue to stir 20h at 35 ℃; By the colloid obtaining 100 ℃ of crystallization 24h in autoclave, use a large amount of deionized water wash after being cooled to room temperature, at 60 ℃, be dried into powder.
Second step: get powder and Fe (NO that mass ratio is 0.4:1
3)
39H
2more than O grinds half hour in mortar, insert in tube furnace after ground, first 350 ℃ of calcining 3h under nitrogen atmosphere, 1 ℃/min to 900 ℃ then, then calcine 3h, can obtain iron oxide bearing and Zero-valent Iron ZCS.
From TEM figure, can find out that under differing temps, iron is all written on mesoporous silicon more uniformly.After the small-angle diffraction proof of XRD is carried iron, material has still kept mesoporous good order, and the diffraction peak explanation of wide-angle has existing with alpha-ferric oxide and zeroth order fe.Figure is at P/P in nitrogen absorption
0for there being IV class hysteretic loop between 0.4-0.7, illustrate and still can make adding of iron material keep meso pore characteristics, graph of pore diameter distribution shows that material aperture is in 6nm left and right.
Claims (3)
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Cited By (3)
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| CN107243358A (en) * | 2017-06-09 | 2017-10-13 | 北京农学院 | A kind of nanoscale zero-valent siderophore and preparation method and application |
| WO2017219793A1 (en) * | 2016-06-20 | 2017-12-28 | 广东工业大学 | Short-pore ordered mesoporous carbon-loaded sulfur-indium-cobalt and sulfur-indium-nickel ternary composite photocatalyst, preparation method therefor, and application thereof |
| CN110051857A (en) * | 2019-04-17 | 2019-07-26 | 华侨大学 | A kind of preparation method and applications of the degradable mesoporous silica nano-particle of bimetal-doped multi-panel |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017219793A1 (en) * | 2016-06-20 | 2017-12-28 | 广东工业大学 | Short-pore ordered mesoporous carbon-loaded sulfur-indium-cobalt and sulfur-indium-nickel ternary composite photocatalyst, preparation method therefor, and application thereof |
| US10661255B2 (en) | 2016-06-20 | 2020-05-26 | Guangdong University Of Technology | Short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst, the preparation method thereof and the use thereof |
| CN107243358A (en) * | 2017-06-09 | 2017-10-13 | 北京农学院 | A kind of nanoscale zero-valent siderophore and preparation method and application |
| CN107243358B (en) * | 2017-06-09 | 2020-02-21 | 北京农学院 | A kind of nanoscale zero-valent siderophore and its preparation method and application |
| CN110051857A (en) * | 2019-04-17 | 2019-07-26 | 华侨大学 | A kind of preparation method and applications of the degradable mesoporous silica nano-particle of bimetal-doped multi-panel |
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Application publication date: 20140205 |