CN103272643A - Preparation method of high-load-capacity metal phthalocyanine catalyst - Google Patents
Preparation method of high-load-capacity metal phthalocyanine catalyst Download PDFInfo
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- CN103272643A CN103272643A CN2013102277866A CN201310227786A CN103272643A CN 103272643 A CN103272643 A CN 103272643A CN 2013102277866 A CN2013102277866 A CN 2013102277866A CN 201310227786 A CN201310227786 A CN 201310227786A CN 103272643 A CN103272643 A CN 103272643A
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Abstract
The invention discloses a preparation method of a high-load-capacity metal phthalocyanine catalyst. The method comprises the following steps: dissolving metal phthalocyanine in concentrated sulfuric acid having a mass percentage of 70-100%, adding a carrier stabilizing concentrated sulfuric acid for loading, adding water for diluting, collecting a loaded metal phthalocyanine catalyst, washing, and drying to obtain a composite catalyst having a load capacity of 0-60%. The method has the advantages of high load capacity, simple process, low cost, high yield, and suitableness for the industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of high capacity amount metal phthalocyanine catalyst.
Background technology
Metal phthalocyanine compound chemical stability height has performances such as good heat-resisting, sun-proof, acidproof, alkaline-resisting, bright and lustrous, strong adhesion, at first by widely as pigment, dye well printing and dyeing industry.Metal phthalocyanine compound is easy to preparation, Stability Analysis of Structures, is easy to modification and load, nonpoisonous and tasteless, also present good performance at aspects such as electric conductivity, chemical catalysis, photoelectric effect, liquid crystal display, gas sensitizing effect, phototherapy medicament, phototropic even nonlinear optical materials, be used to many important techniques field, as aspects such as industrially desulfurized, fabric oxidative decoloration, sewage disposal, air pollutants degradeds.
Metal phthalocyanine is the complex compound that constitutes centered by metal, the atom of molecule inner frame structure is substantially in a plane, metal ion or the atom of center is in " semi-nudity " state, easily the s track of the d track that is full of with its part, adjacent higher one deck or track bonding formation complex ion or the molecule of p track and ligand molecule, atom or ion can substitute part metals, metal oxide, slaine as some catalyst for reaction.In addition, because it is insoluble to common organic solvent, metal phthalocyanine can separate from reaction system by the method for filtering.Therefore, metal phthalocyanine shows excellent catalytic effect as the heterogeneous catalysis of many reactions, can be used as the catalyst of tens of kinds of organic reactions, as decarboxylic reaction, oxidation reaction, reduction reaction, decomposition reaction, hydrogen exchange reaction, multi-component reaction, electrochemical reaction, hydroxylating etc.
The support type heterogeneous catalysis separates easily and reuses, and reduces catalyst to the pollution of environment, and can keep the efficient catalytic performance, saves cost.Chinese invention patent application CN 1900411 A disclose a kind of metal phthalocyanine loaded fiber and preparation method with catalytic activity; Chinese invention patent application CN 101590428 A disclose a kind of sulfonic acid iron-phthalocyanine through the preparation method of mesoporous molecular sieve supported catalyst, and it can utilize visible-light activated its intermediate factory effluent of hydrogen peroxide catalytic degradation dye well; Chinese invention patent application CN 101590429 A disclose a kind of sulfonic acid iron-phthalocyanine through resin-carried Preparation of catalysts method, and it can utilize visible light photocatalytic degradation of organic pollutants; Chinese invention patent application CN 101070680 A disclose a kind of binuclear metallo phthalocyanine through the preparation method of fibrous material supported catalyst, and its PARA FORMALDEHYDE PRILLS(91,95) has good elimination effect; Yet traditional carrying method is that metal phthalocyanine is dissolved in organic solvent, adds loading substrate and adsorbs.The method is subjected to that metal phthalocyanine solubility in organic solvent is low, to condition restriction such as a little less than the affinity of metal phthalocyanine, the gained catalyst loadings is lower, generally can only reach 5% effect, has limited its range of application in organic solvent for loading substrate.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high capacity amount metal phthalocyanine catalyst is to overcome the low deficiency of metal phthalocyanine loaded amount in the prior art.
Implementation procedure of the present invention is as follows:
A kind of preparation method of high capacity amount metal phthalocyanine catalyst may further comprise the steps:
(1) metal phthalocyanine being dissolved in mass percent concentration is 70～100% the concentrated sulfuric acid;
(2) adding is carried out load to the stable carrier of the concentrated sulfuric acid, and described carrier is selected from active carbon, CNT, zeolite, silica gel, diatomite, titanium dioxide, is preferably active carbon;
(3) thin up is collected load-type metal phthalocyanine catalyst, washing, dry getting final product, and the most handy organic or inorganic aqueous slkali washing of washing process is to alkalescence.
Can obtain the load-type metal phthalocyanine catalyst of load capacity 0 ~ 60% by above-mentioned carrying method.
Described metal phthalocyanine structure shown in general formula (I),
M is Mg, Mn, Fe, Co, Ni, Cu, Ag or Zn;
R
1～R
16Be independently selected from-H-Et ,-OCH
3,-COOH ,-NO
2,-F ,-Cl ,-Br ,-I ,-Ph.
Advantage of the present invention and good effect: (1) adopts the inventive method, can access the catalyst of high capacity amount, and load capacity can be regulated 0 ~ 60%; (2) adopt the catalyst of the inventive method preparation suitable multiple to the stable load material of acid, gained catalyst efficient height; (3) technology of the present invention is simple, cost is low, productive rate is high, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is tetranitro FePC load type active carbon catalyst decomposes H
2O
2The active testing installation drawing;
Fig. 2 is tetranitro FePC load type active carbon catalyst decomposes H
2O
2Activity curve.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Specifically, the present invention is after a certain amount of metal phthalocyanine is added concentrated sulfuric acid heating for dissolving, cooling adds a certain amount of carrier, utilizes carrier compatibility to metal phthalocyanine in sulfuric acid to adsorb load more by force, thin up then, deposit centrifugally, aqueous slkali is washed till alkalescent, washing, dry, obtain the metal phthalocyanine loaded type catalyst of load capacity 0 ~ 60%.
Embodiment 1
(M is Cu in the general structure, R to take by weighing the 1.0g CuPc
1～R
16Be H), add in the 100mL beaker, add 10mL 80% concentrated sulfuric acid, be warming up to 80 ℃ of dissolvings, after the cooling, add active carbon 9.0g under stirring in batches, continue to stir 0.5h.In mixed liquor impouring 100mL water, stir, deposition, centrifugal, washing, 1% K
2CO
3Solution is washed till alkalescent, and washing is centrifugal.120 ℃ of oven dry down get load capacity and are about 10% CuPc load type active carbon.
Similar to Example 1, different is selects the 3.0g CuPc for use (M is Cu in the general structure, R
1～R
16For-NO
2), carrier is CNT (7.0g), gets load capacity and is about 30% CuPc load CNT.
Carrier is replaced with zeolite, silica gel, diatomite or titanium dioxide, can prepare the loaded catalyst of different carriers.
Metal is Mg in the metal phthalocyanine, Mn, and Co, Ni, Ag or Zn also are easy to prepare by existing known method.
(M is Fe in the general structure, R to take by weighing the 1.0g FePC
1～R
16Be H), add in the 100mL beaker, add 10mL 98% concentrated sulfuric acid, be warming up to 80 ℃ of dissolvings, after the cooling, add active carbon 9.0g under stirring in batches, continue to stir 0.5h.In mixed liquor impouring 100mL water, stir, deposition, centrifugal, washing, the ammonia spirit of 1M is washed till alkalescent, and washing is centrifugal.120 ℃ of oven dry down get load capacity and are about 10% FePC load type active carbon.
(M is Fe in the general structure, R to take by weighing 1.0g tetranitro FePC
2,6 (7), 10 (11), 14 (15)Be NO
2, all the other R are H), add in the 100mL beaker, add 10mL 98% concentrated sulfuric acid, be warming up to 80 ℃ of dissolvings, after the cooling, add active carbon 9.0g under stirring in batches, continue to stir 0.5h.In mixed liquor impouring 100mL water, stir, deposition, centrifugal, washing, 1% K
2CO
3Solution is washed till alkalescent, and washing is centrifugal.120 ℃ of oven dry down get load capacity and are about 10% tetranitro FePC load type active carbon.
(M is Fe in the general structure, R to take by weighing 2.0g tetranitro FePC
2,6 (7), 10 (11), 14 (15)Be NO
2, all the other R are H), add in the 100mL beaker, add 10mL 98% concentrated sulfuric acid, be warming up to 80 ℃ of dissolvings, after the cooling, add active carbon 8.0g under stirring in batches, continue to stir 0.5h.In mixed liquor impouring 100mL water, stir, deposition, centrifugal, washing, 1% K
2CO
3Solution is washed till alkalescent, and washing is centrifugal.120 ℃ of oven dry down get load capacity and are about 20% tetranitro FePC load type active carbon.
(M is Fe in the general structure, R to take by weighing 4.0g tetranitro FePC
2,6 (7), 10 (11), 14 (15)Be NO
2, all the other R are H), add in the 100mL beaker, add 10mL 98% concentrated sulfuric acid, be warming up to 80 ℃ of dissolvings, after the cooling, add active carbon 6.0g under stirring in batches, continue to stir 0.5h.In mixed liquor impouring 100mL water, stir, deposition, centrifugal, washing, 1% K
2CO
3Solution is washed till alkalescent, and washing is centrifugal.120 ℃ of oven dry down get load capacity and are about 40% tetranitro FePC load type active carbon.
Embodiment 6: tetranitro FePC load type active carbon decomposing H
2O
2The active testing experiment.
As shown in Figure 1, connect constant pressure funnel at 50 mL conical flasks, funnel is suitable for reading to be connected with the U-shaped pipe that has scale, takes by weighing the tetranitro FePC load type active carbon (preparation of embodiment 4-6 method) of 2 mg different loads amounts, add in the conical flask, pipette 10.00 mL, 3% H
2O
2In constant pressure funnel, the testing fixture air-tightness.Open magnetic agitation, record A pipe or B pipe initial volume value.Open constant pressure funnel, with H
2O
2Put into conical flask, pick up counting this moment, read bulking value behind 3 min, and according to Volume Changes value curve plotting, as shown in Figure 2, tetranitro FePC load type active carbon is to H
2O
2Decomposition good catalytic effect is arranged, load capacity is about at 40% o'clock, catalyzing and decomposing H
2O
2Activity the highest.
Use CuPc load type active carbon decomposing H
2O
2The active same high catalytic effect that obtains.
Claims (5)
1. the preparation method of a high capacity amount metal phthalocyanine catalyst is characterized in that may further comprise the steps:
(1) metal phthalocyanine being dissolved in mass percent concentration is 70～100% the concentrated sulfuric acid;
(2) adding is carried out load to the stable carrier of the concentrated sulfuric acid;
(3) thin up is collected load-type metal phthalocyanine catalyst, washing, dry getting final product.
2. according to the preparation method of the described metal phthalocyanine catalyst of claim 1, it is characterized in that: described metal phthalocyanine structure shown in general formula (I),
M is Mg, Mn, Fe, Co, Ni, Cu, Ag or Zn;
R
1～R
16Be independently selected from-H-Et ,-OCH
3,-COOH ,-NO
2,-F ,-Cl ,-Br ,-I ,-Ph.
3. according to the preparation method of the described metal phthalocyanine catalyst of claim 1, it is characterized in that: described carrier is selected from active carbon, CNT, zeolite, silica gel, diatomite, titanium dioxide.
4. according to the preparation method of the described metal phthalocyanine catalyst of claim 3, it is characterized in that: described carrier is active carbon.
5. according to the preparation method of the described metal phthalocyanine catalyst of claim 1, it is characterized in that: in the step (3), with the washing of organic or inorganic aqueous slkali.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437639A (en) * | 2014-12-25 | 2015-03-25 | 东华大学 | Method of preparing green advanced water treatment chemicals with carbon nano-tube compounded tetrasulfophthalocyanine |
| CN104759259A (en) * | 2015-04-02 | 2015-07-08 | 河北科技大学 | Metal phthalocyanine supported adsorbent as well as preparation method and use thereof |
| CN104926713A (en) * | 2015-05-24 | 2015-09-23 | 西北大学 | Synthetic method of polysubstitution 1,2,5,6-tetrahydropyridine compound |
| CN111370712A (en) * | 2020-02-24 | 2020-07-03 | 中南大学 | Preparation method of high-activity electrochemical oxygen reduction catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437639A (en) * | 2014-12-25 | 2015-03-25 | 东华大学 | Method of preparing green advanced water treatment chemicals with carbon nano-tube compounded tetrasulfophthalocyanine |
| CN104759259A (en) * | 2015-04-02 | 2015-07-08 | 河北科技大学 | Metal phthalocyanine supported adsorbent as well as preparation method and use thereof |
| CN104926713A (en) * | 2015-05-24 | 2015-09-23 | 西北大学 | Synthetic method of polysubstitution 1,2,5,6-tetrahydropyridine compound |
| CN111370712A (en) * | 2020-02-24 | 2020-07-03 | 中南大学 | Preparation method of high-activity electrochemical oxygen reduction catalyst |
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Application publication date: 20130904 |