CN100528756C - Ordered spherical large mesoporous material alpha-Fe2O3 - Google Patents

Ordered spherical large mesoporous material alpha-Fe2O3 Download PDF

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CN100528756C
CN100528756C CNB2007100662651A CN200710066265A CN100528756C CN 100528756 C CN100528756 C CN 100528756C CN B2007100662651 A CNB2007100662651 A CN B2007100662651A CN 200710066265 A CN200710066265 A CN 200710066265A CN 100528756 C CN100528756 C CN 100528756C
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mesoporous
polymethylmethacrylate
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CN101172645A (en
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王彤文
常桥稳
刘玲
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Yunnan Normal University
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Abstract

The invention relates to an ordered ball type big mesoporous Alpha-Fe2O3 material, belonging to the technical filed of material preparation. The ball type big mesoporous Alpha-Fe2O3 material with an aperture diameter of 37 plus or minus 3nm and an aperture wall of 12 plus or minus 2nm, which orderly extends along the three-dimensional direction, is obtained by taking the polymethacrylic methyl rosmarinate milk-globule the ball diameter of which is 71 plus or minus 5nm and the colloidal crystals which are closely accumulated and distributed along the three-dimensional direction as templates, and through dipping the templates by the ethanol-water mixture of FeC2O4.2H2O, and then removing the PMMA templates through heating, solidifying and roasting. The structure and the magnetic performance of the big mesoporous are determined into a novel ordered ball type big mesoporous Alpha-Fe2O3 material through SEM, TEM, XRD and N2 adsorption test and squid. The material of the invention has the advantages of crystal aperture wall, particular ball type big mesoporous and weak ferromagnetism. The material can be used for preparing for catalyst and sensor.

Description

A kind of orderly spherical large mesoporous α-Fe 2O 3Material
Technical field:
The present invention relates to adopt a kind of polyalcohol colloid crystal template method of littleization of sphere diameter, preparation has the spherical large mesoporous Fe of three-dimensional order of weak ferromagnetism energy 2O 3Material belongs to technical field of material.
Background technology:
The template-directed synthetic method has been widely used in creating the ordered porous material of different structure and yardstick [1]Up to the present, can synthesize silicon oxide, silico-aluminate, aluminate or phosphate and associated materials effectively with meso-hole structure [2-4]Yet the transition metal oxide material that preparation has meso-hole structure has certain degree of difficulty, and previous synthetic work adopts the soft template method more, as being surfactant molecule template or the block copolymer template under the auxiliary agent by part, has successfully synthesized Nb 2O 5, TiO 2, ZrO 2, WO 3And mesoporous material such as MnOx [5-8]In recent years, utilize wide-aperture mesopore silicon oxide for template (as SBA-15 [9]), adopt the nanometer foundry engieering, can synthesize order mesoporous transition metal oxide material with high-crystallinity [10-13]Yet also there is limitation in this method, will carry out in HF or NaOH solution as removing of silicon oxide template, thereby limit the expansion of hole wall component.
Iron oxide material is the material of class widespread use in catalysis, magnetic device and electrochemical appliance, and the iron oxide material of functionalization has low-cost and hypotoxic characteristics [14], porous Fe with unordered or order mesoporous structure 2O 3Can be prepared by the method for soft template and hard template [15,16], the mesoporous Fe of these method preparations 2O 3Its mesoporous pore size distribution range is at 3-10nm.
The colloidal crystal template technology can expand the range scale in aperture the macropore scope of 1mm to from 50nm, and this colloidal crystal template can be waited by silicon oxide colloid ball, polymeric colloid milk-globule or other nanocrystals to be formed [17,18],, can prepare various components and have the spherical macroporous structure material that three-dimensional order is arranged by to the duplicating of this template [19]For example, be the colloidal crystal template that the polystyrene milk-globule of 760 ± 25nm is arranged by adopting sphere diameter, reproduciblely go out aperture and the pore wall thickness macropore Fe of 550 ± 20nm and 60 ± 10nm respectively 2O 3Material [20]Yet, can copy the aperture by a kind of polyalcohol colloid crystal template microsphere of littleization of sphere diameter and remain challenging problem at the transition metal oxide material of mesoporous scope.
Up to the present, Shang Weijian is relevant to create pore diameter range at 30-40nm (being called mesoporous greatly herein) by the polyalcohol colloid crystal mould plate technique, and has the spherical large mesoporous Fe that three-dimensional order is arranged 2O 3The preparation report of material.Also do not see the aperture at 37 ± 3nm, hole wall is the spherical large mesoporous Fe of 12 ± 2nm 2O 3The magnetic characteristic report of network.
Reference:
[1]Soler-illia，G.J.D.；Sanchez，C.；Lebeau，B.；Patarin，J.Chem.Rev.2002，102，4093.
[2]Corma，A.Chem.Rev.1997，97，2373.
[3]Stein，A.；Melde，B.J.；Schroden，R.C.Adv.Mater.2000，12，1403.
[4]Cundy，C.S.；Cox，P.A.Chem.Rev.2003，103，663.
[5]Antonelli，D.M.；Ying，J.Y.Angew.Chem.，Int.Ed.Engl.1995，34，2014.
[6]Antonelli，D.M.；Nakahira，A.；Ying，J.Y.Inorg.Chem.1996，35，3126.
[7]Tian，Z.；Tong，W.；Wang，J.；Duan，N.；Krishnan，V.V.；Suib，S.L.Science?1997，276，926.
[8]Yang，P.；Zhao，D.；Margolese，D.l.；Chmelka，B.F.；Stucky，G.D.Nature?1998，396，152.
[9]Zhao，D.Y.；Huo，Q.S.；Feng，J.L.；Chmelka，B.F.；Stucky，G.D.J.Am.Chem.Soc.1998，120，6024.
[10]Ryoo，R.；Joo，S.H.；Kruk，M.；Jaroniec，M.Adv.Mater.2001，13，677.
[11]Lee，J.S.；Joo，S.H.；Ryoo，R.J.Am.Chem.Soc.2002，124，1156.
[12]Zhu，K.K.；Yue，B.；Zhou，W.Z.；He，H.Y.Chem.Commun.2003，1，98.
[13]Dickinson，C.；Zhou，W.Z.；Hodgkins，R.P.；Shi，Y.F.；Zhao，D.Y.；He，H.Y.Chem.Mater.2006，18，3088.
[14]Jiao，F.；Yue，B.；Zhu，K.K.；Zhao，D.Y.；He，H.Y.Chem.Lett.2003，32，770.
[15]Brezesinski，T.；Groenewolt，M.；Antonietti，M.；Smarsly，B.Angew.Chem.，Int.Ed.2006，45，781
[16]Jiao，F.；Harrison，A.；Jumas，J.-C.；Chadwick，A.V.；Kockelmann，W.；Bruce，P.G.J.Am.Chem.Soc.2006，128，5468.
[17]Wijnhoven，J.E.G.J.；Vos，W.L.Science?1998，281，802.
[18]Holland，B.T.；Blanford，C.F.；Stein，A.Science?1998，281，538.
[19]Holland，B.T.；Blanford，C.F.；Do，T.；Stein，A.Chem.Mater.1999，11，795.
[20]Yan，H.；Blanford，C.F.；Holland，B.T.；Smyrl，W.H.；Stein，A.Chem.Mater.2000，12，1134.
Summary of the invention:
The object of the present invention is to provide and adopting a kind of sphere diameter is that the colloidal crystal that polymethylmethacrylate (PMMA) the milk-globule close-packed of 71 ± 5nm is arranged is a template, and preparation has spherical large mesoporous α-Fe that weak ferromagnetism energy and tool three-dimensional order are arranged 2O 3Material.
It is that the PMMA milk-globule colloidal crystal that close-packed is arranged on three-dimensional of 71 ± 5nm is a template that the present invention adopts sphere diameter, with FeC 2O 42H 2O is dissolved in water and the alcoholic acid mixing solutions, with this solution impregnation template, to reach the gap of abundant filling template milk-globule, after being heating and curing, removes the PMMA template by roasting, obtains piling up gap location at original PMMA milk-globule and forms solid Fe 2O 3Skeleton hole wall network, at the spherical pore in formation hole, the position of original PMMA milk-globule, it is that formed Fe is duplicated in the original PMMA milk-globule counter-rotating that close-packed is arranged on three-dimensional that this spherical pore can be seen as 2O 3Tangible contraction has taken place in skeleton when thermal treatment, forming a kind of aperture is 37 ± 3nm, and hole wall is 12 ± 2nm, and the spherical large mesoporous structure of extending in order on three-dimensional.
The present invention has utilized the three-dimensional ordered macroporous spherical template method of general establishment, and (sphere diameter is 71 ± 5nm) polymkeric substance milk-globule colloidal crystal template, creates the ordered porous transition metal oxide material of aperture less than 50nm but adopted littleization of sphere diameter.Than general mesoporous transition metal oxide material, utilize the vesicular structure that polymkeric substance milk-globule this " accurate hard template " caused owing to have bigger mesoporous aperture and thicker pore wall thickness, phenomenon can be avoided usually when preparation metal oxide meso-hole structure, the big meso-hole structure of high-crystallinity can be under corresponding thermal treatment temp, obtained having because the caused meso-hole structure of thermal treatment caves in.This big mesoporous method cost of PMMA polyalcohol colloid crystal milk-globule template for preparing transition metal oxide of littleization of sphere diameter that utilizes is low, and operational condition is easy to control, is a kind of cheapness, simple method.
Adopt SEM, TEM, XRD, N 2This Fe has been determined in the adsorption-desorption experiment 2O 3Big mesoporous structure adopts superconducting quantum interference device (SQUID) (SQUID) to measure big mesoporous Fe 2O 3Magnetic property, for a kind of weak ferromagnetism energy and at the spherical large mesoporous iron oxide material of three-dimensional ordered arrangement.
By the SEM image of Fig. 1 as seen, the PMMA colloid micro ball presents closely packed ordered arrangement on three-dimensional, and the mean diameter of PMMA colloid micro ball is defined as 71 ± 5nm by the SEM striograph.
By the SEM image of Fig. 2 as seen, formed Fe 2O 3Replica presents a kind of network structure of hole, hole arrangement of three-dimensional order, the position in hole, hole is the position of original PMMA colloid micro ball, determine that by the SEM image its aperture, hole is 37 ± 3nm (being called mesoporous greatly herein), hole wall is 12 ± 2nm, the sphere diameter of the original PMMA colloid micro ball of the aperture ratio that is produced is little, illustrate that contraction taken place obvious when roasting the PMMA/ oxide component, shrinking percentage is 48%.
Fig. 3 has further provided sample at the TEM image that does not absorb on direction, as along [100] direction (Fig. 3 a and Fig. 3 b) and [111] direction (Fig. 3 c).These images further show this big mesoporous orderly pore passage structure, and this image is quite similar in the macropore Fe that is reported 2O 3TEM image (document 19 sees reference).
The crystalline structure of this hole wall is further determined by wide-angle x-ray diffraction figure (Fig. 4), distinguishable characteristic diffraction peak has appearred in the XRD among Fig. 4, the data of these characteristic diffraction peaks and JCPDS card No.33-0664 match, and are a kind of rhombohedral α-Fe 2O 3(
Figure C20071006626500061
Figure C20071006626500062
), show that the synthetic sample has α-Fe 2O 3The crystalline state hole wall structure.Adopt the Scherrer formula that The grain size is calculated as 13nm.
The hole adsorpting characteristic of sample is by the N of Fig. 5 2The adsorption-desorption thermoisopleth determines that thermoisopleth shows as a kind of typical VI adsorpting characteristic, at relatively high pressure scope (P/P 0＞0.75) precipitous holding high appears, and follow the hysteresis loop of a broadness, this mainly is because the big mesoporous institute in the sample causes, corresponding BJH graph of pore diameter distribution (Fig. 6) also provides a kind of most probable and is distributed in the interior pore distribution feature of 20-40nm scope, the pore size distribution of this broadness is because the average result that melange effect caused in the gap between the spherical pore of the opening of spherical pore and accumulation and the hole window between the hole (the hole window can be defined as 15-25nm less than opening by SEM) and the spherical pore accumulation.This high pressure range isothermal hold high and broad pore size distribution also appear in the report of many big-pore mesoporous preparation of metal oxides (as referring to document, Li, W.C.; Lu, A.H.; Weidenthaler, C.; Sch ü th, F.Chem.Mater.2004,16,5676), and for aperture and the pore wall thickness macropore Fe of 550 ± 20nm and 60 ± 10nm respectively 2O 3The thermoisopleth that material occurred then is a typical II type adsorption isothermal line (referring to reference 20).BET specific surface area after this sample roasting is 91.2m 2g -1, than the spherical macropore Fe that is reported 2O 3Material (aperture: 550 ± 20nm, specific surface area 39m 2g -1, referring to reference 20) and want high, but than having a mesoporous α-Fe of cystalline order hole wall structure by the preparation of hard template nanometer foundry engieering 2O 3(aperture: 3.85nm, BET specific surface area: 139m 2g -1, referring to reference 16) and low.
The magnetic property of sample adopts superconducting quantum interference device (SQUID) (SQUID) to be measured.Fig. 7 be the field cooling specific magnetising moment curve of sample under 0.1T (Field-cooled magnetization, FC) and null field cooling specific magnetising moment curve (zero-field-cooled magnetization, ZFC).As can be seen from the figure: the FC curve raises with the reduction of temperature, and is to occur a flex point about 75K in temperature, does not have block Fe 2O 3The sign that the normal the sort of Morin that occurs of material shifts; A broad peak appearred in the ZFC curve when the most significant susceptibility feature appeared at and is 78K near temperature, and when temperature is lower than 78K, FC curve and ZFC curve separately, these magnetization characteristic and all with the short grained α-Fe of those nanometers 2O 3Material or the mesoporous α-Fe for preparing by hard template nanometer foundry engieering 2O 3(reference 16) is quite similar, has the Morin transfer of inhibition and the obstruction transfer (this sample is 78K) that has some forms at the temperature place that depends on the structurally associated yardstick, and this big mesoporous Fe is described 2O 3Sample is a kind of weak ferromagnetism material at low temperatures.This magnetic property further determines that by the magnetic hysteresis loop of sample Fig. 8 is the magnetic hysteresis loop of this sample under 5K, occurs tangible hysteresis loop among the figure, its coercive force is 477Oe, when temperature is elevated to 298K, and hysteresis loop narrow down (Fig. 9), coercive force drops to 77Oe, and big mesoporous Fe is described 2O 3Sample at room temperature ferromegnetism decreases.
Material of the present invention is compared with current material, has advantages such as crystalline state hole wall and special spherical large mesoporous network and weak ferromagnetism energy, can be used for preparing catalyzer and transmitter.
Description of drawings:
Fig. 1 is field emission scanning electron microscope (SEM) striograph of PMMA colloidal crystal template.
Fig. 2 is big mesoporous α-Fe 2O 3The field emission scanning electron microscope of sample (SEM) striograph.
Fig. 3 is big mesoporous α-Fe 2O 3The transmission electron microscope of sample (TEM) striograph.Fig. 3 a and b: along [100] direction, Fig. 3 c:[111] direction.
Fig. 4 is big mesoporous α-Fe 2O 3The X-ray diffraction of sample (XRD) figure.
Fig. 5 is big mesoporous α-Fe 2O 3The N of sample 2The adsorption-desorption thermoisopleth.
Fig. 6 is big mesoporous α-Fe 2O 3Sample corresponding to N 2The isothermal BJH graph of pore diameter distribution of adsorption-desorption.
Fig. 7 is big mesoporous α-Fe 2O 3Field cooling specific magnetising moment curve (FC) and the null field cooling specific magnetising moment curve (ZFC) of sample under 0.1T.
Fig. 8 is big mesoporous α-Fe 2O 3The magnetic hysteresis loop figure of sample under 5K.
Fig. 9 is big mesoporous α-Fe 2O 3The magnetic hysteresis loop figure of sample under 298K.
Embodiment:
Orderly spherical large mesoporous Fe of the present invention 2O 3Material employing sphere diameter is that the colloidal crystal that the close-packed of PMMA milk-globule on three-dimensional of 71 ± 5nm arranged is a template, passes through FeC 2O 42H 2The alcohol-water mixing solutions dipping template of O is heating and curing, and roasting is removed the PMMA template and obtained, and it is 37 ± 3nm that this material has the aperture, and hole wall is 12 ± 2nm, and the spherical large mesoporous constitutional features of extending in order on three-dimensional.This material is obtained by the following step:
A. in 175mL distilled water, add 0.05g SDS, under magnetic agitation, add the 15mL methyl methacrylate monomer, feeding nitrogen more than 20 minutes, to remove stopper, is dissolved in 0.1164g Potassium Persulphate initiator in the 20mL distilled water in this solution, add then in this solution, under 70 ℃, magnetic agitation reaction 2 hours obtains white milk sap, under 3000 rotating speeds, centrifugal settling obtains polymethylmethacrylate (PMMA) colloidal crystal template after 6 hours.
B. with 2g FeC 2O 42H 2O joins in the 5mL distilled water, under the magnetic agitation, add 2g oxalic acid, dripping hydrogen peroxide to solid dissolves fully, add 5mL ethanol (the choosing preparation with solution of this precursor) again, above-mentioned drips of solution is added on 70 ℃ of dry down PMMA colloidal crystal templates of crossing, soaked 2-3 minute referring to reference 20, suction filtration, drying at room temperature.
C. adopt the roasting method of temperature programming to remove PMMA template in the sample, temperature rise rate: 1 ℃ of min -1, when rising to 310 ℃, temperature kept 5 hours, kept 10 hours at 450 ℃ then, obtain orderly spherical large mesoporous Fe 2O 3Product.

Claims (1)

1. orderly spherical large mesoporous α-Fe 2O 3Material, employing sphere diameter are that the colloidal crystal that the polymethylmethacrylate milk-globule of 71 ± 5nm is arranged in the three-dimensional close-packed is a template, pass through FeC 2O 42H 2The alcohol-water mixing solutions of O dipping template is heating and curing, and roasting obtains after removing the polymethylmethacrylate template, and it is characterized in that this material is: the aperture is 37 ± 3nm, and hole wall is 12 ± 2nm, and the spherical large mesoporous α-Fe that arranges in the up preface of three-dimensional 2O 3Material; This material is obtained by the following step:
A. in 175mL distilled water, add the 0.05g sodium lauryl sulphate, add the 15mL methyl methacrylate monomer under the magnetic agitation, feeding nitrogen more than 20 minutes, to remove stopper, is dissolved in 0.1164g Potassium Persulphate initiator in the 20mL distilled water in this solution, add then in this solution, under 70 ℃, magnetic agitation reaction 2 hours obtains white milk sap, under 3000 rotating speeds, centrifugal settling obtains the polymethylmethacrylate colloidal crystal template after 6 hours;
B. with 2gFeC 2O 42H 2O is dissolved in the 5mL distilled water, under the magnetic agitation, adds 2g oxalic acid, drip hydrogen peroxide to solid and dissolve fully, add 5mL ethanol again, above-mentioned drips of solution is added on 70 ℃ of down dry polymethylmethacrylate colloidal crystal templates of crossing, soaked suction filtration, drying at room temperature 2-3 minute;
C. adopt the roasting method of temperature programming to remove polymethylmethacrylate template in the sample, temperature rise rate: 1 ℃ of min -1, when rising to 310 ℃, temperature kept 5 hours, kept 10 hours at 450 ℃ then, obtain orderly spherical large mesoporous α-Fe 2O 3Product.
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CN102167291A (en) * 2011-03-18 2011-08-31 复旦大学 Method for preparing mesoporous metal oxide through pyrolysis of oxalate
CN103523833A (en) * 2013-09-25 2014-01-22 天津大学 Preparation method of nano ferric oxide (Fe2O3) for acetone gas sensor material
CN104617290B (en) * 2013-11-04 2017-02-08 中国科学院大连化学物理研究所 Homogenous precipitation method for preparing Fe2O3 nanobelt and Fe2O3 nanobelt-carbon composite material
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