CN104071756B - A kind of MnO 2the preparation method of intercalation hydrotalcite-like composite material - Google Patents

A kind of MnO 2the preparation method of intercalation hydrotalcite-like composite material Download PDF

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CN104071756B
CN104071756B CN201410283975.XA CN201410283975A CN104071756B CN 104071756 B CN104071756 B CN 104071756B CN 201410283975 A CN201410283975 A CN 201410283975A CN 104071756 B CN104071756 B CN 104071756B
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hydrotalcite
mno
composite material
preparation
intercalation
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CN104071756A (en
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范彬彬
杨磊
史秀锋
白亚东
李瑞丰
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Taiyuan University of Technology
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Abstract

The invention discloses a kind of MnO 2the preparation method of intercalation hydrotalcite-like composite material, first houghite roasting is formed mixed metal oxide, again with mixed metal oxide described in the toluene solution process of the organosilane containing mercapto functional group, after organosilane grafting is on mixed metal oxide, add KMnO 4in the aqueous solution, utilize the memory effect of houghite, make mixed metal oxide at KMnO 4in the aqueous solution, hydration recovers its laminate structure, and utilizes the vattability of institute's grafting mercapto functional group, will be inserted into the MnO of houghite interlayer 4 -?reduction forms MnO 2, thus prepare MnO 2intercalation hydrotalcite-like composite material.MnO prepared by the present invention 2intercalation hydrotalcite-like composite material can be applied to the fields such as electrode materials, electrochemical capacitance material and catalytic material.

Description

A kind of MnO 2the preparation method of intercalation hydrotalcite-like composite material
Technical field
The present invention relates to a kind of preparation method of hydrotalcite-like composite material, particularly relate to one and there is MnO 2the preparation method of the hydrotalcite-like composite material of intercalation.
Background technology
Houghite compound (hydrotalcite-likecompound, HTLc) be made up of positively charged layers of metal hydroxides and interlayer charge balance anion, similar brucite (Brucite), therefore be referred to as again layered double hydroxide (layereddoublehydroxide, LDH).Under normal circumstances, this compounds is by the Mg (OH) being mutually total to limit 2octahedra laminate structure is stacked, as part Mg top by hydrogen bond association 2+by the Tricationic of similar radius (as Al 3+, Fe 3+and Cr 3+) isomorphous substitution time, can cause the accumulation of positive charge on layer, these positive charges are positioned at the negatively charged ion of interlayer (as CO 3 2-) balance, its complementary space of interlayer is then filled by crystal water.Its general formula is expressed as: [M 2+ 1-xm 3+ x(OH) 2] x+[X m-] x/mnH 2o(M is metal, and X is interlayer negatively charged ion, 0.2 ﹤ x ﹤ 0.4).Composition and the very wide negatively charged ion of range of choice in adjustable layer, for HTLc material provides wide application prospect, not only can be used for preparing anionite, sorbent material and catalyzer, also can be used for preparing solid nano reactor and polymer composites [G.Centi, S.Perathoner microporousMesoporousMater., 107 (2008) 3; L.Wang, C.Li, M.Liu, D.G.Evans, X.Duan, chem.Commun., 2 (2007) 123; D.G.David, X.Duan, chem.Commun., 5 (2006) 485].
The anionresin performance that houghite has is provide favourable condition to the object that its Intercalation reaction is different, the object negatively charged ion of number of different types is successfully inserted in hydrotalcite layers by the method for anionresin, prepare the multiple matrix material with different-shape and characteristic, and these matrix materials are successfully applied in the field [K.M.Parida such as chromatogram, chemistry or biosensor, magneticsubstance and catalytic material, M.Sahoo, S.Singa j.Catal.276 (2010) 161; S.Gago, M.Pillinger, A.A.Valente, T.M.Santos, J.Rocha, I.S.Goncalves, inorg.Chem.43 (2004) 5422; S.Li, J.Lu, M.Wei, D.G.Evans, X.Duan, Adv.Func.Mater.20 (2010) 2848; D.G.Evans, X.Duan, chem.Commun.(2006) 485; B.M.Choudary, N.S.Chowdari, M.L.Kantam, K.V.Raghavan, j.Am.Chem.Soc.123 (2001) 9220].But limitting by hydrotalcite-like compound feature, the object inserted is mainly the electronegative compound such as inorganic anion, organic anion, anionic polymer.Electroneutral metal oxide then owing to lacking electrostatic adelphotaxy, cannot effectively be inserted houghite interlayer, be which greatly limits the preparation of metal oxide/HTLc matrix material.
MnO 2be a kind of metal oxide with several functions, have broad application prospects in fields such as battery material, electrochemical capacitance material, electrode and catalytic materials.By MnO 2being inserted into houghite interlayer, is improve MnO 2performance and a kind of effective way preparing advanced composite material.Liu etc. adopt the multistep process such as insertion, reduction and heating, have prepared MnO 2pillared NiFe hydrotalcite-like composite material [H.J.Li, G.Zhu, Z.P.Yang, Z.L.Wang, Z.H.Liu, j.colloidInterf.Sci.345 (2010) 228].This composite material exhibits goes out good capacitive property, but the preparation process of matrix material is comparatively complicated, relates to NiFe-CO 3hTLc synthesizes; With HCl process by interlayer CO 3 2-be replaced into Cl -; Use KMnO again 4solution processes, and makes Cl -with MnO 4 -carry out exchanging and with MnCl 2by MnO 4 -reduce; And the process such as last calcination process.Above-mentioned preparation method is not only loaded down with trivial details, and with HCl process HTLc, the structure of destructible HTLc, particularly for MgAlHTLc.Diao etc. for matrix, utilize Co with CoAlHTLc material 2+and MnO 4 -between redox reaction, prepared MnO 2/ CoAlHTLc matrix material [Z.P.Diao, Y.X.Zhang, X.D.Hao, Z.Q.Wen, ceram.Int.40 (2014) 2115].This material also shows good electrochemical behavior, but its preparation method is only limitted to CoAlHTLc material, and MnO 2be difficult to be inserted into HTLc interlayer.Therefore, design and development one prepares MnO 2the novel method of intercalation HTLc matrix material is very necessary.
Summary of the invention
The object of the invention is based on existing preparation MnO 2the deficiency that intercalation hydrotalcite-like composite material exists, provides a kind of MnO 2the preparation method of intercalation hydrotalcite-like composite material.
MnO of the present invention 2the preparation method of intercalation hydrotalcite-like composite material comprises:
A) roasting houghite is to form mixed metal oxide;
B) with mixed metal oxide described in the toluene solution process of the organosilane containing mercapto functional group, to obtain silanization hydrotalcite precursor;
C) described silanization hydrotalcite precursor is added KMnO 4in the aqueous solution, prepare MnO 2intercalation hydrotalcite-like composite material.
In the above-mentioned preparation method of the present invention, the houghite used has with [M 2+ 1-xm 3+ x(OH) 2] x+[X m-] x/mnH 2the general structure that O represents, in general formula, M is metal, wherein M 2+for Mg 2+, Zn 2+, Cu 2+, Ni 2+in one, or wherein several arbitrarily mixing, M 3+for Al 3+or Cr 3+; X is interlayer negatively charged ion, can be CO 3 2-, NO 3 -or Cl -.
Preferably, in described general structure, M 2+/ M 3+mol ratio is between 2 ~ 10.
In aforesaid method, it is 250 ~ 550 DEG C by the maturing temperature that described houghite roasting forms mixed metal oxide.
Further, describedly silanization hydrotalcite precursor is prepared and at KMnO 4the process processing silanization hydrotalcite precursor in the aqueous solution is all carry out under the protection of rare gas element.
Preferably, the described organosilane containing mercapto functional group is mercapto propyl group organoalkoxysilane, comprises mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, mercapto hydroxypropyl methyl dimethoxysilane etc.
MnO of the present invention 2intercalation hydrotalcite-like composite material further preparation method is:
A) by described houghite in air atmosphere at 250 ~ 550 DEG C roasting obtain mixed metal oxide;
B) getting described mixed metal oxide joins in the anhydrous toluene solution of thiohydroxy-containing group's organosilane, and back flow reaction 12 ~ 24h under protection of inert gas, obtains silanization hydrotalcite precursor after ethanolic extraction, drying;
C), under protection of inert gas, described silanization hydrotalcite precursor is joined KMnO 4in the aqueous solution, stirring reaction 12 ~ 24h, obtains MnO 2intercalation hydrotalcite-like composite material.
Preferably, described KMnO 4the concentration of the aqueous solution is 0.01 ~ 0.1mol/L.
Wherein, described with KMnO 4the process of aqueous solution process silanization hydrotalcite precursor all can be carried out within the scope of room temperature ~ 100 DEG C.
MnO of the present invention 2houghite roasting is first formed mixed metal oxide by the preparation method of intercalation hydrotalcite-like composite material, again by the organosilane grafting containing mercapto functional group on mixed metal oxide, utilize the memory effect of houghite, make mixed metal oxide at KMnO 4in the aqueous solution, hydration recovers its laminate structure, and utilizes the vattability of institute's grafting mercapto functional group, will be inserted into the MnO of houghite interlayer 4 -reduction forms MnO 2, thus prepare MnO 2intercalation hydrotalcite-like composite material.
Prepare MnO in the process of the present invention 2intercalation hydrotalcite-like composite material, preparation technology is simple, goes for dissimilar HTLc material; MnO 2be inserted into HTLc interlayer, and by the grafting amount of modulation silane and KMnO 4the concentration modulation MnO of solution 2intercalation amount.
MnO prepared by the present invention 2intercalation hydrotalcite-like composite material can be applied to the fields such as electrode materials, electrochemical capacitance material and catalytic material.
MnO of the present invention 2intercalation hydrotalcite-like composite material has Mn base active sites and Br nsted basic sites two kinds of catalysiss simultaneously, can the multiple oxidizing reaction of catalysis, is particularly the oxidizing reaction of oxygen source with molecular oxygen.Such as, the MnO prepared by the present invention 2intercalation hydrotalcite-like composite material can demonstrate good catalytic performance in the reaction of dioxygen oxidation Preparation of ethylbenzene methyl phenyl ketone.Experiment proves, in normal pressure solvent-free system, use molecular oxygen is oxygen source, tertbutyl peroxide is inductor, MnO of the present invention 2intercalation hydrotalcite-like composite material is catalyzer, and in 5h, the transformation efficiency of ethylbenzene reaches 29.5%, and methyl phenyl ketone selectivity reaches 94.7%.
Accompanying drawing explanation
Fig. 1 is MnO prepared by embodiment 1 2the XRD spectra of intercalation MgAl-HTLc matrix material.
Fig. 2 is MnO prepared by embodiment 1 2the XPS spectrum figure of Mn in intercalation MgAl-HTLc matrix material.
Embodiment
Embodiment 1
60mL is contained 120mmolMg (NO 3) 26H 2o and 30mmolAl (NO 3) 39H 2the mixed salt solution instillation 70mL of O contains 90mmolNa 2cO 3the aqueous solution in, drip 2mol/LNaOH solution adjust ph simultaneously and make it constant in 11, gained white suspension is poured in tetrafluoroethylene reactor, in 120 DEG C of crystallization 10h.Gained precipitation, must containing the MgAl-HTLc sample of carbonate anion through deionized water wash, filtration, drying.By this HTLc roasting 10h at 550 DEG C in air atmosphere, obtain MgAl mixed oxide.
Get the above-mentioned MgAl mixed oxide of 1g and join 15mL containing in the anhydrous toluene solution of 1mmol mercaptopropyl trimethoxysilane, reflux under protection of inert gas 12h, subsequently ethanolic extraction 12h, obtains silanization hydrotalcite precursor after drying.
Under protection of inert gas, described silanization hydrotalcite precursor is joined 50mL0.1mol/LKMnO 4in the aqueous solution, stirred at ambient temperature 24h, after washing, filtration, vacuum-drying, obtains MnO 2intercalation MgAl hydrotalcite-like composite material.
The XPS spectrum figure of the XRD spectra of gained sample and wherein Mn is shown in Fig. 1 and Fig. 2 respectively.
Can see from XRD spectra, MnO 2intercalation MgAl hydrotalcite-like composite material shows the characteristic peak of hydrotalcite structure, and peak intensity is low.Do not observe MnO 2characteristic diffraction peak, MnO in matrix material is described 2for amorphous state or high dispersing uniform state.
XRD spectra shows, MnO 2in intercalation MgAl hydrotalcite-like composite material, Mn2p 3/2and Mn2p 1/2bimodally lay respectively at 642.2eV and 653.4eV, this and bibliographical information MnO 2b.E. value consistent [M.Nakayama, A.Tanaka, S.Konishi, K.Ogura, j.Mater.Res.19 (2004) 1509], illustrate that manganese is with MnO in the composite 2state layer between exist.
N 2adsorption-desorption test adopts U.S.'s Kang Ta company (Quantachrome) NOVA1200E type specific surface area and aperture tester, before test by sample at 250 DEG C of vacuum activating 3h, with high-purity N 2for adsorbate, under-196 DEG C of (liquid nitrogen) conditions, carry out adsorption-desorption experiment.
In normal pressure solvent-free system, use molecular oxygen is oxygen source, tertbutyl peroxide is inductor, and the present embodiment matrix material is catalyzer, reaction conditions: ethylbenzene 33mmol, catalyzer 0.2g, O 2flow 5mL/min, temperature of reaction 130 DEG C, tertbutyl peroxide 30mg, reaction times 5h.
N 2absorption representation and catalytic result are summarized in table 1.In 5h, conversion of ethylbenzene reaches 29.5%, and methyl phenyl ketone selectivity reaches 94.7%.
aresult comes from N 2adsorption-desorption is analyzed.
bresult calculates according to Fe content in catalyzer.
Embodiment 2
60mL is contained 90mmolCu (NO 3) 23H 2o and 20mmolAl (NO 3) 39H 2the mixed salt solution instillation 70mL of O contains 90mmolNa 2cO 3the aqueous solution in, drip 2mol/LNaOH solution adjust ph simultaneously and make it constant in 11, gained suspension is poured in tetrafluoroethylene reactor, in 60 DEG C of crystallization 24h.Gained precipitation, must containing the CuAl-HTLc sample of carbonate anion through deionized water wash, filtration, drying.By this HTLc roasting 15h at 450 DEG C in air atmosphere, obtain CuAl mixed oxide.
Get the above-mentioned CuAl mixed oxide of 1g and join 15mL containing in the anhydrous toluene solution of 3mmol mercaptopropyltriethoxysilane, reflux under protection of inert gas 12h, subsequently ethanolic extraction 12h, obtains silanization hydrotalcite precursor after drying.
Under protection of inert gas, described silanization hydrotalcite precursor is joined 50mL0.1mol/LKMnO 4in the aqueous solution, at 40 DEG C, stir 12h, after washing, filtration, vacuum-drying, obtain MnO 2intercalation CuAl hydrotalcite-like composite material.
Embodiment 3
60mL is contained 60mmolMg (NO 3) 26H 2o, 60mmolCu (NO 3) 23H 2o and 30mmolAl (NO 3) 39H 2the mixed salt solution instillation 70mL of O contains 90mmolNa 2cO 3the aqueous solution in, drip 2mol/LNaOH solution adjust ph simultaneously and make it constant in 11, gained suspension is poured in tetrafluoroethylene reactor, in 80 DEG C of crystallization 20h.Gained precipitation, must containing the MgCuAl-HTLc sample of carbonate anion through deionized water wash, filtration, drying.By this HTLc roasting 10h at 400 DEG C in air atmosphere, obtain MgCuAl mixed oxide.
Get the above-mentioned MgCuAl mixed oxide of 1g and join 15mL containing in the anhydrous toluene solution of 1mmol mercaptopropyl trimethoxysilane, reflux under protection of inert gas 12h, subsequently ethanolic extraction 12h, obtains silanization hydrotalcite precursor after drying.
Under protection of inert gas, described silanization hydrotalcite precursor is joined 50mL0.025mol/LKMnO 4in the aqueous solution, at 80 DEG C, stir 24h, after washing, filtration, vacuum-drying, obtain MnO 2intercalation MgCuAl hydrotalcite-like composite material.
Embodiment 4
60mL is contained 150mmolZn (NO 3) 26H 2o and 30mmolAl (NO 3) 39H 2the mixed salt solution instillation 70mL of O contains 90mmolNa 2cO 3the aqueous solution in, drip 2mol/LNaOH solution adjust ph simultaneously and make it constant in 11, gained white suspension is poured in tetrafluoroethylene reactor, in 100 DEG C of crystallization 15h.Gained precipitation, must containing the ZnAl-HTLc sample of carbonate anion through deionized water wash, filtration, drying.By this HTLc roasting 10h at 500 DEG C in air atmosphere, obtain ZnAl mixed oxide.
Get the above-mentioned ZnAl mixed oxide of 1g and join 15mL containing in the anhydrous toluene solution of 1mmol mercaptopropyltriethoxysilane, reflux under protection of inert gas 12h, subsequently ethanolic extraction 12h, obtains silanization hydrotalcite precursor after drying.
Under protection of inert gas, described silanization hydrotalcite precursor is joined 50mL0.05mol/LKMnO 4in the aqueous solution, stirred at ambient temperature 24h, after washing, filtration, vacuum-drying, obtains MnO 2intercalation ZnAl hydrotalcite-like composite material.
Embodiment 5
120mL is contained 250mmolMg (NO 3) 26H 2o, 50mmolNi (NO 3) 26H 2o and 30mmolAl (NO 3) 39H 2the mixed salt solution instillation 300mL of O contains 90mmolNa 2cO 3the aqueous solution in, drip 2mol/LNaOH solution adjust ph simultaneously and make it constant in 11, gained suspension is poured in tetrafluoroethylene reactor, in 120 DEG C of crystallization 2h.Gained precipitation, must containing the MgNiAl-HTLc sample of carbonate anion through deionized water wash, filtration, drying.By this HTLc roasting 5h at 550 DEG C in air atmosphere, obtain MgNiAl mixed oxide.
Get the above-mentioned MgNiAl mixed oxide of 1g and join 15mL containing in the anhydrous toluene solution of 2mmol mercaptopropyl trimethoxysilane, reflux under protection of inert gas 12h, subsequently ethanolic extraction 12h, obtains silanization hydrotalcite precursor after drying.
Under protection of inert gas, described silanization hydrotalcite precursor is joined 50mL0.05mol/LKMnO 4in the aqueous solution, at 80 DEG C, stir 24h, after washing, filtration, vacuum-drying, obtain MnO 2intercalation MgNiAl hydrotalcite-like composite material.
Embodiment 6
60mL is contained 60mmolMg (NO 3) 26H 2o and 30mmolAl (NO 3) 39H 2the mixed salt solution instillation 70mL of O contains 90mmolNaNO 3the aqueous solution in, drip 2mol/LNaOH solution adjust ph simultaneously and make it constant in 10, gained white suspension is poured in tetrafluoroethylene reactor, in 120 DEG C of crystallization 24h.Gained precipitation, must containing the MgAl-HTLc sample of nitrate anion through deionized water wash, filtration, drying.By this HTLc roasting 8h at 500 DEG C in air atmosphere, obtain MgAl mixed oxide.
Get the above-mentioned MgAl mixed oxide of 1g and join 15mL containing in the anhydrous toluene solution of 1mmol mercaptopropyltriethoxysilane, reflux under protection of inert gas 24h, subsequently ethanolic extraction 12h, obtains silanization hydrotalcite precursor after drying.
Under protection of inert gas, described silanization hydrotalcite precursor is joined 50mL0.1mol/LKMnO 4in the aqueous solution, stirred at ambient temperature 24h, after washing, filtration, vacuum-drying, obtains MnO 2intercalation MgAl hydrotalcite-like composite material.
Embodiment 7
60mL is contained 60mmolNi (NO 3) 26H 2o and 15mmolAl (NO 3) 39H 2the mixed salt solution instillation 70mL of O contains in the aqueous solution of 60mmolNaCl, drips 2mol/LNaOH solution adjust ph simultaneously and makes it constant in 10, poured into by gained suspension in tetrafluoroethylene reactor, in 65 DEG C of crystallization 18h.Gained precipitation, through deionized water wash, filtration, drying, obtains the NiAl-HTLc sample of chloride ion-containing.By this HTLc roasting 10h at 400 DEG C in air atmosphere, obtain NiAl mixed oxide.
Get the above-mentioned NiAl mixed oxide of 1g and join 15mL containing in the anhydrous toluene solution of 1mmol mercaptopropyl trimethoxysilane, reflux under protection of inert gas 12h, subsequently ethanolic extraction 12h, obtains silanization hydrotalcite precursor after drying.
Under protection of inert gas, described silanization hydrotalcite precursor is joined 50mL0.1mol/LKMnO 4in the aqueous solution, stirred at ambient temperature 24h, after washing, filtration, vacuum-drying, obtains MnO 2intercalation NiAl hydrotalcite-like composite material.
Embodiment 8
60mL is contained 60mmolMg (NO 3) 26H 2o and 30mmolCr (NO 3) 39H 2the mixed salt solution instillation 50mL of O contains 20mmolNa 2cO 3the aqueous solution in, drip 2mol/LNaOH solution adjust ph simultaneously and make it constant in 9, gained suspension is poured in tetrafluoroethylene reactor, in 65 DEG C of crystallization 18h.Gained precipitation, must containing the MgCr-HTLc sample of carbonate anion through deionized water wash, filtration, drying.By this HTLc roasting 10h at 250 DEG C in air atmosphere, obtain MgCr mixed oxide.
Get the above-mentioned MgCr mixed oxide of 1g and join 15mL containing in the anhydrous toluene solution of 1mmol mercaptopropyltriethoxysilane, reflux under protection of inert gas 12h, subsequently ethanolic extraction 12h, obtains silanization hydrotalcite precursor after drying.
Under protection of inert gas, described silanization hydrotalcite precursor is joined 50mL0.05mol/LKMnO 4in the aqueous solution, at 100 DEG C, stir 4h, after washing, filtration, vacuum-drying, obtain MnO 2intercalation MgCr hydrotalcite-like composite material.

Claims (9)

1. a MnO 2the preparation method of intercalation hydrotalcite-like composite material, comprising:
A) roasting houghite is to form mixed metal oxide;
B) with mixed metal oxide described in the toluene solution process of the organosilane containing mercapto functional group, to obtain silanization hydrotalcite precursor;
C) described silanization hydrotalcite precursor is added KMnO 4in the aqueous solution, prepare MnO 2intercalation hydrotalcite-like composite material;
Described houghite has with [M 2+ 1-xm 3+ x(OH) 2] x+[X m-] x/mnH 2the general structure that O represents, in general formula, M is metal, wherein M 2+for Mg 2+, Zn 2+, Cu 2+, Ni 2+in one, or wherein several arbitrarily mixing, M 3+for Al 3+or Cr 3+; X is interlayer negatively charged ion, is CO 3 2-, NO 3 -or Cl -.
2. MnO according to claim 1 2the preparation method of intercalation hydrotalcite-like composite material, is characterized in that in described hydrotalcite-like compound general formula, M 2+/ M 3+mol ratio is 2 ~ 10.
3. MnO according to claim 1 2the preparation method of intercalation hydrotalcite-like composite material, is characterized in that described roasting houghite is 250 ~ 550 DEG C to form the maturing temperature of mixed metal oxide.
4. MnO according to claim 1 2the preparation method of intercalation hydrotalcite-like composite material, is characterized in that describedly preparing silanization hydrotalcite precursor and at KMnO 4the process processing silanization hydrotalcite precursor in the aqueous solution is all carried out under protection of inert gas.
5. MnO according to claim 1 2the preparation method of intercalation hydrotalcite-like composite material, is characterized in that the described organosilane containing mercapto functional group is mercapto propyl group organoalkoxysilane.
6. MnO according to claim 5 2the preparation method of intercalation hydrotalcite-like composite material, is characterized in that described mercapto propyl group organoalkoxysilane is mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane or mercapto hydroxypropyl methyl dimethoxysilane.
7. MnO according to claim 1 2the preparation method of intercalation hydrotalcite-like composite material, is characterized in that described preparation method is:
A) by described houghite in air atmosphere at 250 ~ 550 DEG C roasting obtain mixed metal oxide;
B) getting described mixed metal oxide joins in the anhydrous toluene solution of thiohydroxy-containing group's organosilane, and back flow reaction 12 ~ 24h under protection of inert gas, obtains silanization hydrotalcite precursor after ethanolic extraction, drying;
C), under protection of inert gas, described silanization hydrotalcite precursor is joined KMnO 4in the aqueous solution, stirring reaction 12 ~ 24h, obtains MnO 2intercalation hydrotalcite-like composite material.
8. the MnO according to claim 1 or 7 2the preparation method of intercalation hydrotalcite-like composite material, is characterized in that described KMnO 4the concentration of the aqueous solution is 0.01 ~ 0.1mol/L.
9. the MnO according to claim 1 or 7 2the preparation method of intercalation hydrotalcite-like composite material, is characterized in that described with KMnO 4the process of aqueous solution process silanization hydrotalcite precursor is carried out within the scope of room temperature ~ 100 DEG C.
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