CN102335627A - Preparation method of metal complex functionalized hydrotalcite-like nano-layer sheet - Google Patents
Preparation method of metal complex functionalized hydrotalcite-like nano-layer sheet Download PDFInfo
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- CN102335627A CN102335627A CN2011101831206A CN201110183120A CN102335627A CN 102335627 A CN102335627 A CN 102335627A CN 2011101831206 A CN2011101831206 A CN 2011101831206A CN 201110183120 A CN201110183120 A CN 201110183120A CN 102335627 A CN102335627 A CN 102335627A
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Abstract
The invention relates to a preparation method of a metal complex functionalized hydrotalcite-like nano-layer sheet, which belongs to the field of physical chemistry and material chemistry. The preparation method comprises the following steps of: utilizing metal complex functionalized silane to be directly reacted with surface hydroxyl on a hydrotalcite-like nano-layer sheet after stripping a layer so as to graft a metal complex on the hydrotalcite-like nano-layer sheet, and simultaneously utilizing the reaction of the silane and the surface hydroxyl and the electronic and three-dimensional effects of the grafted metal complex to weaken the electrostatic interaction between the stripped layer and the nano-layer sheet, thereby improving the stability of the hydrotalcite-like nano-layer sheet, preventing the hydrotalcite-like nano-layer sheet from being compounded after a solvent is removed, and still keeping the state of the nano-layer sheet. An organic-inorganic composite material prepared by adopting the method has the characteristics of large specific surface area and high content of the metal complex, and simultaneously has the multifunctional catalytic performances of hydrotalcite-like and the metal complex.
Description
Technical field
The preparation method of the functionalized acrylic/hydrotalcite-like nano synusia of metal complex of the present invention; The category that belongs to physical chemistry and materials chemistry; Be specifically related to the silane that metal complex is functionalized and directly react, prepare and have the composite organic-inorganic material that specific area is big, metal complex content height has houghite and many catalysis of metal complex characteristics simultaneously with surface hydroxyl on the acrylic/hydrotalcite-like nano synusia of stripping layer.
Background technology
Houghite compound (hydrotalcite-like compound; HTLc) be to constitute by positively charged layers of metal hydroxides and interlayer charge balance anion; Structure similar water magnesite (Brucite); So be referred to as again layered double hydroxide (layered double hydroxide, LDH).Generally, this compounds is by the Mg (OH) that is total to the limit each other
2Octahedra stratiform structure through hydrogen bond association to the top stack.As part Mg
2+By the Tricationic of similar radius (like Al
3+, Fe
3+And Cr
3+) when the isomorphous replaces, can cause the accumulation of layer last positive charge, these positive charges are positioned at the anion of interlayer (like CO
3 2-) balance, and at its complementary space of interlayer, then fill by the crystallization water.The general formula of HTLc can be expressed as: [M
2+ 1-xM
3+ x(OH)
2] [X
M-]
X/mNH
2O (M is a metal, and X is the interlayer anion, 0.2＜x＜0.4).Composition and the very wide interlayer intercalant anion of range of choice provide wide application prospect for the HTLc material in the adjustable layer; Not only can be used for preparing anionite, adsorbent and catalyst; Also can be used for preparing solid nano reactor and polymer composites [G.Centi; S.Perathoner, Microporous MesoporousMater., 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].Metal complex is good homogeneous catalyst, the effectively multiple reaction of catalysis under temperate condition, but, make its application receive certain restriction because homogeneous catalyst is in use existing is difficult to separate with product and many deficiencies such as can not reuses.Metal complex is carried on prepares heterogeneous catalysis on the solid carrier, is an important channel of realizing heterogeneousization of homogeneous catalysis, also is the important content of Green Chemistry research.The anion exchange performance that HTLc had and the scalability of interfloor distance are for the insertion of anion metal complex provides advantage.Employing anion exchange methods such as S.Bhattachrjee are inserted into chirality sulphonato-MnSalen among the Zn-Al HTLc; This catalyst shows high reaction activity and high and enantioselectivity [S.Bhattachariee in the asymmetric epoxidation reaction of alkene; J.A.Anderson; Adv.Synth.Catal., 348 (2006) 151].M.Halma etc. adopt coprecipitation in the synthetic system of Zn-Al HTLc, to add the ferriporphyrin anionic complex, and original position is inserted into [M.Halma, K.Castro in the Zn-Al HTLc layer with anionic complex; C.Taviot-Gueho, V.Pr é vot, C.Forano; F.Wypych; S.Nakagaki, J.Catal., 233 (2008) 257].Yet limit by the architectural feature of HTLc; The metal complex that no matter adopts which kind of method to insert is necessary for electronegative metal complex; Other metal complex then can't be inserted into the HTLc interlayer owing to lack the static adelphotaxy effectively, this just to a great extent limit the kind and the range of application of prepared metal complex/HTLc composite.In addition, a subject matter that in the process of preparation metal complex HTLc intercalation material, is run into is that the insertion amount is less, has greatly limited its application [T.Hibino, W.Jones, J.Mater.Chem., 11 (2001) 1321 owing to receive diffusion restriction; M.Adachi-Pagano, C.Forano, J.Besse, J.Mater.Chem., 13 (2003) 1988.].In order to make insert fully get into interlayer, HTLc is shelled layer handle that to make all surface of HTLc all come out be the effective way that addresses this problem.In this simultaneously; From the angle of HTLc as catalyst and catalyst carrier; The stripping layer is handled and also can be increased the specific area of catalyst and the accessibility of active sites greatly, and positive role [S.Liu, X.Jiang are played in the improvement of catalyst performance; G.Zhuo, J.Mol.Catal.A:Chem.290 (2008) 72.].Because stronger electrostatic interaction between HTLc layer and the layer is carried out very difficulty of splitting to it in water or in other nonaqueous solvents.People have carried out some fruitful work aspect the peeling off of HTLc material in recent years, through synthetic HTLc material with high-crystallinity, insert the anion (as: dodecyl sulphate root) of large-size and in certain solvent by refluxing or sonicated; Can Al base HTLc effectively be peeled off [R.Ma, Z.Liu, K.Takada; N.Lyi, Y.Bando, T.Sasaki; J.Am.Chem.Soc., 129 (2007) 5257.; A.Park, H.Kwon, A.Woo, S.Kim, Adv.Mater.17 (2005) 106.].Though the acrylic/hydrotalcite-like nano synusia after peeling off has very high specific area, can only exist in solution with the form of emulsion, in case can spontaneous recovery original structure except that after desolvating through drying.This specific character of hydrotalcite nano synusia makes in its modification that is mainly used in polymer, and is difficult to nano ply directly as catalyst or catalyst carrier.Why HTLc nano ply after peeling off can recover original structure is owing to have stronger interaction between its layer and the layer, this stronger interaction can through interlayer insert macromolecular material increase layer with layer between distance or employing silylating reagent make it means such as hydroxyl with the HTLc nano ply reacts and effectively weakened.The researcher has carried out some research work at this on the one hand; For example: employings such as F.Wypych are carried out modification with APTS (triethoxy amine propyl silane) to the Mg-Al HTLc of dodecyl sulphate root intercalation in toluene solution, through anion exchange with electronegative ferriporphyrin carry out load or with the APTS end group-NH
2For reaction position through containing the reaction of F-periphery substituting group ferriporphyrin with neutrality, prepared the functionalized HTLc nano ply of ferriporphyrin [M.Halma, S.Nakagaki, J.Catal.234 (2005) 431. for F.Wypych, A.Bai].But the suitable metal complex with electronegative property of this method loads on the HTLc nano ply; And not enough below existing for the load neutral metal complex: 1) macromolecular surfactant anion difficulty remove; Obstruction is utilized HTLc nanometer laminate, catalytic performance that particularly can not fine performance HTLc laminate in the preparation of multifunction catalyst; 2) APTS of grafting on HTLc nanometer laminate limits and diffusion restriction owing to receiving space multistory with the reaction between the metal complex; Not only difficultly carry out but also be difficult to the two quantitative relation of control causing the ligancy of central ion of institute's load iron metalloporphyrin uncertain, and then influence the catalytic performance of made supported catalyst.
Summary of the invention
Preparation method's purpose of the functionalized acrylic/hydrotalcite-like nano synusia of metal complex of the present invention is: based on HTLc as material of main part in immobilized homogeneous catalyst-metal complex with good catalytic performance existing range of choice finite sum to metal complex owing to receive the inter-level diffusion restriction; The metal complex insertion amount uncertain grade of ligancy low and institute's carried metal complex central ion is mainly not enough; Thereby disclose a kind of adopt the functionalized silane of metal complex directly with the HTLc nano ply on the surface hydroxyl method of reacting improve the stability of HTLc nano ply and the load capacity of metal complex, prepare the method for the functionalized HTLc nano ply multifunctional material of metal complex.
The preparation method of the functionalized acrylic/hydrotalcite-like nano synusia of metal complex of the present invention is characterized in that concrete steps are:
I, at first will contain the ethanol solution of diethylenetriamine, and join in the ethanol solution that contains salicylide, and in the inert gas shielding refluxed, obtain part N, N-bis (salicyledene) diethylenetriamine is called for short saldien;
II, secondly with triethoxy chloropropyl silane; The ethanol solution that is called for short CPTM joins in the prepared saldien ethanol solution of I, behind the 3～10h that refluxes, adds the ethanol solution that is dissolved with Schweinfurt green, cobalt acetate, vanadic sulfate or manganese acetate again; Continue the 2～10h that refluxes; After the solvent removed in vacuo, obtain the functionalized silane of required metal presence of Schiff-base complex, be designated as Msaldien-CPTM (M=Cu
2+, Co
2+, VO
3+Or Mn
2+);
III, with N, dinethylformamide or formamide solvent join among MgAl or the ZnAl HTLc, under the sonicated condition, shell layer; Interaction between the HTLc synusia is weakened, form the HTLc nano ply, wherein the mol ratio of Mg/Al or Zn/Al is between 10 and 2; The mass volume ratio of MgAl or ZnAl HTLc and solvent is less than 20g/L; The sonicated time is 0.5～6 hour, and the sonicated temperature is room temperature～60 ℃, and ultrasonic power is 40～100W;
IV, under inactive gas protection; The functionalized silane of metal complex that II is prepared joins the N of the prepared HTLc nano ply of III; In the colloid of dinethylformamide or formamide, heated and stirred makes the hydroxyl on functionalized silane of metal complex and the HTLc nano ply carry out grafting, and wherein heating-up temperature is 60～140 ℃; Time is 2～15 hours, and its said inactive gas is argon gas, nitrogen or helium.
The preparation method of the functionalized acrylic/hydrotalcite-like nano synusia of above-mentioned metal complex is characterized in that MgAl HTLc or the intercalant anion among the ZnAl HTLc selected for use are nitrate anion, glycine root or dodecyl sulphate root.
Its advantage of preparation of the functionalized acrylic/hydrotalcite-like nano synusia of metal complex of the present invention is: this method is not only utilized the reaction between silylating reagent and the HTLc nano ply surface hydroxyl to reduce concentration of surface hydroxyl groups significantly, strengthens hydrophobicity performance, is reduced the possibility of recombinating between peel ply; But also the space of metal complex capable of using and stereoeffect strengthen the difficulty of reorganization between layer and the layer, to prevent that effectively the HTLc nano ply from reorganization taking place have positive effect in dry run; Secondly, adopt the prepared multi-functional catalysis material of this method not only to integrate the dual catalytic function of HTLc and metal complex but also have the higher available specific surface and the accessibility of active sites; The 3rd, do not receive the restriction of HTLc design feature, can be immobilized in HTLc with having a metal complex of different nature, and can guarantee that the central atom of institute's carried metal complex has definite ligancy; The 4th, owing to reduce the load capacity that the diffusional resistance of interlayer can effectively improve metal complex in the made composite.
Description of drawings
The XRD spectra of MgAl HTLc (b) sample that Fig. 1 MgAl HTLc (a), Cusaldien are functionalized
The DRS spectrogram of the MgAl HTLc that Fig. 2 Cusaldien is functionalized
The specific embodiment
Realize that embodiment of the present invention is following:
Embodiment 1
At first; 10mL is contained the ethanol solution of 1mmol diethylenetriamine, join in the 5mL ethanol solution that contains the 2mmol salicylide, behind inert gas shielding refluxed 2h; Obtain part N, N-bis (salicyledene) diethylenetriamine (saldien).Secondly; The ethanol solution 10mL of 1mmol triethoxy chloropropyl silane (CPTM) is joined in the prepared saldien ethanol solution of 1mmol, behind the backflow 3h, add the ethanol solution that 30mL is dissolved with the Schweinfurt green of 1mmol again; Continue backflow 5h; After the solvent removed in vacuo, obtain the functionalized silane of required copper presence of Schiff-base complex, be designated as Cusaldien-CPTM.Then; The MgAl HTLc that with 1g Mg/Al mol ratio is 2 nitrate anion intercalation places 200mLN, under 40 ℃, the sonicated condition of 40W, carries out sonicated 1h in the dinethylformamide, after the centrifugation an even translucent colloid stripping layer liquid; Gained stripping layer liquid is transferred in the there-necked flask; Under inert gas shielding, add 10mL and contain the ethanol solution of the Cusaldien-CPTM of 1mmol, behind 100 ℃ of reaction 10h through dehydration; After centrifugation, absolute ethyl alcohol extracting and drying, obtain the functionalized MgAl HTLc nano ply composite of Cusaldien.The XRD spectra of gained sample and DRS spectrogram are seen accompanying drawing 1 (b) and accompanying drawing 2 respectively.
At first; 50mL is contained the ethanol solution of 5mmol diethylenetriamine, join in the 25mL ethanol solution that contains the 10mmol salicylide, behind inert gas shielding refluxed 4h; Obtain part N, N-bis (salicyledene) diethylenetriamine (saldien).Secondly; The ethanol solution 30mL of 5mmol triethoxy chloropropyl silane (CPTM) is joined in the prepared saldien ethanol solution of 5mmol, behind the backflow 10h, add the ethanol solution that 30mL is dissolved with the Schweinfurt green of 5mmol again; Continue backflow 10h; After the solvent removed in vacuo, obtain the functionalized silane of required copper presence of Schiff-base complex, be designated as Cusaldien-CPTM.Then; With 4g Mg/Al mol ratio is that 10 glycine root intercalation MgAl HTLc places the 200mL formamide under the sonicated condition of room temperature, 100W, to carry out sonicated 6h; Get an even translucent colloid stripping layer liquid after the centrifugation, gained stripping layer liquid is transferred in the there-necked flask, under inert gas shielding; Adding 10mL contains the ethanol solution through the dehydration of metal magnesium rod of 5mmol Cusaldien-CPTM; Behind 140 ℃ of reaction 12h, after centrifugation, absolute ethyl alcohol extracting and drying, obtain the functionalized MgAlHTLc nano ply composite of Cusaldien.
Embodiment 3
At first; 20mL is contained the ethanol solution of 2mmol diethylenetriamine, join in the 10mL ethanol solution that contains the 4mmol salicylide, behind inert gas shielding refluxed 1h; Obtain part N, N-bis (salicyledene) diethylenetriamine (saldien).Secondly; The ethanol solution 10mL of 2mmol triethoxy chloropropyl silane (CPTM) is joined in the prepared saldien ethanol solution of 2mmol, behind the backflow 4h, add the ethanol solution that 30mL is dissolved with the manganese acetate of 2mmol again; Continue backflow 2h; After the solvent removed in vacuo, obtain the functionalized silane of required manganese presence of Schiff-base complex, be designated as Mnsaldien-CPTM.Then; With the 1gMg/Al mol ratio is that 3 glycine root intercalation MgAl HTLc places the 200ml formamide under 60 ℃, the sonicated condition of 60W, to carry out sonicated 0.5h; Get an even translucent colloid stripping layer liquid after the centrifugation, gained stripping layer liquid is transferred in the there-necked flask, under inert gas shielding; Adding 10mL contains the ethanol solution through the dehydration of metal magnesium rod of 2mmol Mnsaldien-CPTM; Behind 120 ℃ of reaction 2h, after centrifugation, absolute ethyl alcohol extracting and drying, obtain the functionalized MgAl HTLc nano ply composite of Mnsaldien
Embodiment 4
At first; 20mL is contained the ethanol solution of 3mmol diethylenetriamine, join in the 15mL ethanol solution that contains the 6mmol salicylide, behind inert gas shielding refluxed 2h; Obtain part N, N-bis (salicyledene) diethylenetriamine (saldien).Secondly; The ethanol solution 20mL of 3mmol triethoxy chloropropyl silane (CPTM) is joined in the prepared saldien ethanol solution of 3mmol, behind the backflow 4h, add the ethanol solution that 40mL is dissolved with the vanadic sulfate of 3mmol again; Continue backflow 10h; After the solvent removed in vacuo, obtain the functionalized silane of required vanadium oxygen presence of Schiff-base complex, be designated as VOsaldien-CPTM.Then; With 2g Mg/Al mol ratio is that 3 glycine root intercalation MgAl HTLc places the 150mL formamide under 50 ℃, the sonicated condition of 80W, to carry out sonicated; Get an even translucent colloid stripping layer liquid after the centrifugation, gained stripping layer liquid is transferred in the there-necked flask, under inert gas shielding; Adding 20mL contains the ethanol solution through the dehydration of metal magnesium rod of the VOsaldien-CPTM of 3mmol; Reaction 15h after centrifugation, absolute ethyl alcohol extracting and drying, obtains the functionalized MgAlHTLc nano ply composite of VOsaldien under 60 ℃.
Embodiment 5
At first; 10mL is contained the ethanol solution of 1mmol diethylenetriamine, join in the 5mL ethanol solution that contains the 2mmol salicylide, behind inert gas shielding refluxed 2h; Obtain part N, N-bis (salicyledene) diethylenetriamine (saldien).Secondly; The ethanol solution 10mL of 1mmol triethoxy chloropropyl silane (CPTM) is joined in the prepared saldien ethanol solution of 1mmol, behind the backflow 4h, add the ethanol solution that 30mL is dissolved with the cobalt acetate of 1mmol again; Continue backflow 10h; After the solvent removed in vacuo, obtain the functionalized silane of required cobalt presence of Schiff-base complex, be designated as Cosaldien-CPTM.Then; With 1g Zn/Al mol ratio is that 3 dodecyl sodium sulfonate root intercalation ZnAl HTLc places the 150mL formamide under 40 ℃, the sonicated condition of 60W, to carry out sonicated; Get an even translucent colloid stripping layer liquid after the centrifugation, gained stripping layer liquid is transferred in the there-necked flask, under inert gas shielding; Adding 10mL contains the ethanol solution through the dehydration of metal magnesium rod of 1mmol Cosaldien-CPTM; Behind reaction 10h under 60 ℃, after centrifugation, absolute ethyl alcohol extracting and drying, obtain the functionalized ZnAl HTLc nano ply composite of Cosaldien.
Claims (2)
1. the preparation method of the functionalized acrylic/hydrotalcite-like nano synusia of metal complex is characterized in that concrete steps are:
I, at first will contain the ethanol solution of diethylenetriamine, and join in the ethanol solution that contains salicylide, and in the inert gas shielding refluxed, obtain part N, N-bis (salicyledene) diethylenetriamine is called for short saldien;
II, secondly with triethoxy chloropropyl silane; The ethanol solution that is called for short CPTM joins in the prepared saldien ethanol solution, behind the 3～4h that refluxes, adds the ethanol solution that is dissolved with Schweinfurt green, cobalt acetate, vanadic sulfate or manganese acetate again; Continue the 2～10h that refluxes; After the solvent removed in vacuo, obtain the functionalized silane of required metal presence of Schiff-base complex, be designated as Msaldien-CPTM (M=Cu
2+, Co
2+, VO
3+Or Mn
2+);
III, with N, dinethylformamide or formamide solvent join among MgAl or the ZnAl HTLc, under the sonicated condition, shell layer; Interaction between the HTLc synusia is weakened, form the HTLc nano ply, wherein the mol ratio of Mg/Al or Zn/Al is between 10 and 2; The mass volume ratio of MgAl or ZnAl HTLc and solvent is less than 20g/L; The sonicated time is 0.5～6 hour, and the sonicated temperature is room temperature～60 ℃, and ultrasonic power is 40～100W;
IV, under inactive gas protection; The functionalized silane of metal complex that II is prepared joins the N of the prepared HTLc nano ply of III; In the colloid of dinethylformamide or formamide, heated and stirred makes the hydroxyl on functionalized silane of metal complex and the HTLc nano ply carry out grafting, and wherein heating-up temperature is 60～140 ℃; Time is 2～15 hours, and its said inactive gas is argon gas or nitrogen.
2. according to the preparation method of the functionalized acrylic/hydrotalcite-like nano synusia of the said metal complex of claim 1, it is characterized in that MgAl HTLc or the intercalant anion among the ZnAl HTLc selected for use are nitrate anion, glycine root or dodecyl sulphate root.
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