CN102671702A - Method for preparing zinc oxide ionic bond grafting and coordination supported tetra(4-carboxyl phenyl) metalloporphyrin catalyst - Google Patents
Method for preparing zinc oxide ionic bond grafting and coordination supported tetra(4-carboxyl phenyl) metalloporphyrin catalyst Download PDFInfo
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- CN102671702A CN102671702A CN201210056641XA CN201210056641A CN102671702A CN 102671702 A CN102671702 A CN 102671702A CN 201210056641X A CN201210056641X A CN 201210056641XA CN 201210056641 A CN201210056641 A CN 201210056641A CN 102671702 A CN102671702 A CN 102671702A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for preparing a zinc oxide ionic bond grafting and coordination supported tetra(4-carboxyl phenyl) metalloporphyrin catalyst. The method comprises the following steps of: dissolving zinc sulfate by using distilled water, and regulating the pH value to 7 to 8 by using a sodium hydroxide solution to obtain Zn(OH)2 turbid liquid; performing suction filtration and washing to obtain a fresh Zn(OH)2 precipitate; conveying the fresh Zn(OH)2 precipitate into a container, keeping the temperature of between 60 and 70 DEG C, dripping an organic solvent in which tetra(4-carboxyl phenyl) metalloporphyrin is dissolved into the precipitate, stirring electrically for 6 to 7 hours, and distilling the solvent out under reduced pressure; and performing the suction filtration, washing, and drying filter cake at the temperature of between 120 and 170 DEG C under vacuum for 6 to 8 hours to obtain the metalloporphyrin-supported catalyst, wherein the catalyst is used for catalyzing and oxidizing methylbenzene, the conversion rate of the methylbenzene is 8.19 percent, the selectivity of aldehyde alcohol is 56.97 percent, and the conversion number of the catalyst is 7.52*10<4>. The catalyst can be recycled effectively for 10 times, and the original catalytic activity is still maintained.
Description
Technical field
The present invention relates to the method for grafting of a kind of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin agent, and with this as catalyst, oxygen catalytic oxidation toluene is produced phenmethylol and benzaldehyde.
Background technology
In current Chemical Manufacture, phenmethylol and benzaldehyde are important Organic Chemicals, and phenmethylol and benzaldehyde are produced in the environmental protection of oxygen catalytic oxidation toluene, have important real Research Significance.In recent ten years, domestic and international many scholars have invented multiple catalysis toluene oxidation technology, and some is also very effective.As: 1.. chlorinolysis: be that raw material carries out chlorination with toluene earlier; Obtain to mix benzyl chloride; Under 70～80 ℃; Usefulness has benzal chloride/zinc salt of 1/2000 approximately as catalyst, and sodium carbonate basic hydrolysis 5～6 h obtain the benzaldehyde that aldehyde is 96～97 % with the thick product purification that obtains at last.This method is former to be the technology of mainly producing benzaldehyde, but because this method course of reaction is grown and is difficult to control, causes equipment corrosion serious, and reacted wastewater is chloride, and is big for environment pollution.Therefore seldom produce benzaldehyde abroad with this method.2.. gaseous oxidation toluene method: adopt fluid bed or fixed bed reactors, use O
2, air or O
3As oxidant, the simple oxide, composite oxides that adopt metal be as catalyst, as: barium oxide; Iron-molybdenum, cobalt-molybdenum, cerium-molybdenum composite oxides; Iron sb oxide and their immobilized thing or the like, reaction temperature are controlled at 350～550 ℃, and pressure is under 0.5～2.5 MPa condition.Vapour phase oxidation process belongs to heterogeneous catalysis process, and its primary product has benzaldehyde, phenmethylol, benzoic acid, hydrocarbon etc.This method benzaldehyde selectivity 20%～80%, toluene conversion are not between 10%～40%, and be and chloride in the product.Because this method is used expensive heavy metal, and environmental pollution is big,
And reaction temperature is high; Deep oxidation easily takes place to be produced and does accessory substance like benzoic acid, phenol, carbon dioxide, carbon monoxide etc. more; The selectivity of benzaldehyde is also difficult to be improved, the conversion ratio that generally needs control toluene less than 4% to obtain higher benzaldehyde selectivity.Therefore the catalyst of developing high activity, high selectivity remains more deep research.3.. the liquid phase oxidation toluene method: the catalyst that this legal system is got benzaldehyde has: one, soluble metal salt class, as: vanadium, iron.With H
2O
2As oxidant, adding other solvent is co-catalyst; Two, the halide of cobalt or manganese or organic acid salt, as, cobalt acetate, manganese acetate etc.With the molecular oxygen is oxidant, and adding bromine is co-catalyst or other solvent.This method toluene conversion 10%-30%; Benzaldehyde and benzyl alcohol selective 10%～90%, owing to added co-catalyst or other solvent of bromine, after reaction finishes; Catalyst is difficult to from mixing physical separation, reclaiming and reuse, and the separation of product is also relatively complicated.
In the organic research of bionic catalysis air oxidation hydro carbons; Artificial template as the cytochrome P-450 enzyme; Metalloporphyrin has great importance, because its reaction condition gentleness, high activity, high selectivity and the feature of environmental protection, the research of metalloporphyrin has enjoyed the concern of Chinese scholars.At solvent-free and no co-catalyst, under 160 ℃ of reaction temperatures, air pressure 0.8MPa, be merely 3.2 * 10 with concentration
-5The tetraphenyl cobalt porphyrin catalytic oxidation toluene of mol/L, toluene conversion is 8.9 %, benzaldehyde and benzyl alcohol selective are 60%.Such homogeneous catalysis system reaction condition is gentle, not plus solvent and additive, to equipment do not have any corrosive atmosphere pollute little, but because the metalloporphyrin homogeneous catalysis system, its free alkali synthesis yield is low, costs an arm and a leg, and is difficult to reclaim and reuses.
At present, the loading problem of metalloporphyrin has become the focus of Chinese scholars research.In order to solve the existing problem of metalloporphyrin homogeneous catalysis system; Improve its stability and catalytic activity; Chinese scholars has been done many work in synthetic and this field of protection metalloporphyrin, and hope is can the synthesis catalytic performance better, the novel metal porphyrin that stability is higher; Also hope to find some good carriers simultaneously; Can not only the pay(useful) load metalloporphyrin and can improve its catalytic activity, prepare and can be fit to the more extensively carried metal porphyrin catalyst of reaction condition, to satisfy the needs of catalysis development on the modern industry.
We once used zinc oxide load four (right-hydroxyl) phenyl cobalt, manganese, ferriporphyrin and four (right-nitro) phenyl cobalt, manganese, ferriporphyrin; Preparation Out-Of-Phase Loading catalyst; The research of catalytic oxidation toluene has obtained result preferably: the per 2.0 mg metalloporphyrins with immobilized are made catalyst, reaction 4h, and the conversion ratio of toluene reaches 7.5 %; The aldehyde alcohol selectivity reaches 78 %, and the turn over number of catalyst reaches 8.8 * 10
4, recyclable repeated use 15 times, and keep the good catalytic performance of catalyst basically.Explain that zinc oxide is a kind of outstanding carrier, on this basis, prepared zinc oxide load four (4-carboxyl phenyl) cobalt, manganese, ferriporphyrin catalyst; Be used for catalytic oxidation toluene; The catalyst equivalent only needs 1.5mg, and the reaction time only needs 3.5 hours, and the conversion ratio of toluene can reach 8.19 %; The aldehyde alcohol selectivity is 56 %, and the catalyst turn over number is 7.52 * 10
4, and catalyst can reclaim effective repeated use at least 10 times, still keeps good catalytic activity.
Summary of the invention
The method that the purpose of this invention is to provide grafting of a kind of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin agent, and with this as catalyst, oxygen catalytic oxidation toluene is produced phenmethylol and benzaldehyde.This catalyst can be produced phenmethylol and benzaldehyde by selective catalytic oxidation toluene, and can reclaim, reuse.Overcome that the conversion per pass that exists in the current toluene oxidation production technology is low, environmental pollution is big, the unit mass metalloporphyrin is difficult to reclaim and the effective low problem of recycling rate of waterused.
The present invention realizes above-mentioned purpose through following technical scheme: the method for grafting of a kind of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin agent comprises the steps:
(1) the fresh Zn (OH) of preparation
2: take by weighing 71 g ZnSO
47H
2O is dissolved in the 300 ml deionized waters, is adjusted to pH=7.5 with the sodium hydroxide solution of 0.3 mol/L, and suction filtration obtains fresh Zn (OH)
2Sediment,
(2) with fresh Zn (OH)
2Sediment through dispersed with stirring in organic solvent; Add the organic solvent that is dissolved with four (4-carboxyl phenyl) metalloporphyrin again, keep 60～70 ℃ of temperature and stir 6～7 h fast, most of solvent is removed in decompression distillation again; Suction filtration, washing; Filter cake obtains grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin agent through 120～170 ℃ of vacuum drying 6～8h, and said organic solvent is acetone and ethanol.
The application of described ionic bond grafting and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin agent; The grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) the catalysis of metalloporphyrin agent that take by weighing 0.5～2.0 mg four (4-carboxyl phenyl) metalloporphyrin equivalent are in 500 ml autoclaves; Add 200 ml cyclohexanes, reaction pressure is controlled at 0.4～0.8 MPa, and temperature is controlled at 160～190 ℃; Mixing speed is controlled at 200～500 rev/mins, and gas flow is 0.04 m
3/ h, after heating arrived reaction temperature, aerating oxygen carried out catalytic oxidation 3.0～4.5 h.
Said zinc oxide load four (4-carboxyl phenyl) metalloporphyrin expression formula is: M TCPP/ZnO
Compare with prior art toluene oxidation technology, outstanding advantage of the present invention is:
1, four (4-carboxyl phenyl) metalloporphyrin with grafting of zinc oxide ionic bond and coordination load is a catalyst; With grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) manganoporphyrin catalyst is example; The catalyst equivalent is 1.5mg only, and selectivity oxygen catalytic oxidation toluene becomes benzaldehyde and phenmethylol.180 ℃ with 0.5MPa under; Reaction 3.5h, catalyst shows good catalytic performance, and metalloporphyrin is immobilized firmly and can reclaim effective repeated use catalysis 10 times; And keep its good catalytic activity; The average conversion of toluene surpasses 7.5 %, and the keto-alcohol average selectivity is higher than 50 %, and the average turn over number of catalyst can reach 7.2 * 10
4And have expensive metal porphyrin and the advantage that shortens the reaction time of saving.
2, grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin dioxygen oxidation toluene is a kind of heterocatalysis; Catalytic activity than metalloporphyrin homogeneous catalysis improves a lot; Can reclaim repeated use and keep its catalytic activity basically, have more Practical significance.This type of ionic bond grafting and coordination supported catalyst synthetic simple easily, immobilized firmly, the product of metalloporphyrin and catalyst easy separation; And reaction condition is gentle; Can be applicable to all kinds of reaction units, metalloporphyrin not only can effectively be protected its not oxidized destruction in reaction through ionic bond grafting and coordination load; Can also improve the recovery repeat usage of catalyst, be a kind of more satisfactory bionical industrial catalyst.
The specific embodiment
Below through embodiment technical scheme of the present invention is described further.
Embodiment 1
The method for preparing grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) cobalt porphyrin catalyst according to the invention: comprise the steps:
(1) the fresh Zn (OH) of preparation
2: take by weighing 71 g ZnSO
47H
2O is dissolved in the 300 ml deionized waters, is adjusted to pH=7.5 with the sodium hydroxide solution of 0.3mol/L, and suction filtration obtains fresh Zn (OH)
2Sediment,
The Zn (OH) that (2) will newly synthesize
2Be scattered in the organic solvent through mechanical agitation; Add the organic solvent that is dissolved with four (4-carboxyl phenyl) metalloporphyrin again; Keep 60 ~ 70 ℃ of temperature and electronic stirring 6 ~ 7 h, most of solvent is removed in decompression distillation again, suction filtration, washing; Filter cake obtains grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin agent through 120 ~ 170 ℃ of vacuum drying 6 ~ 8 h.
Embodiment 2
The method for using of grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) cobalt porphyrin catalyst: have the catalyst of 1.5 mg four (4-carboxyl phenyl) cobalt porphyrin to throw in 500 ml autoclaves grafting of zinc oxide ionic bond and coordination load, add 200 ml toluene.Reaction temperature is 180 ℃, and oxygen pressure is controlled to be 0.7 MPa, and speed of agitator is controlled at 200 rev/mins, and oxygen flow is controlled to be 0.04 m
3/ h, the reaction time is at 3.5 h.The conversion ratio of toluene is 7.33 %, and the aldehyde alcohol selectivity is 51.63 %, and the catalyst turn over number is 6.85 * 10
4
When reaction pressure is 0.5MPa, toluene conversion 7.38 %, selectivity 48.61 %, catalyst turn over number 6.86 * 10
4
Embodiment 3
The method for using of grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) cobalt porphyrin catalyst: have the catalyst of 2.0 mg four (4-carboxyl phenyl) cobalt porphyrin to throw in 500 ml autoclaves grafting of zinc oxide ionic bond and coordination load, add 200 ml toluene.Reaction temperature is 180 ℃, and oxygen pressure is controlled to be 0.6 MPa, and speed of agitator is controlled at 200 rev/mins, and oxygen flow is controlled to be 0.04 m
3/ h, the reaction time is at 3.5 h.The conversion ratio of toluene is 7.62 %, and the aldehyde alcohol selectivity is 48.94 %, and the catalyst turn over number is 5.33 * 10
4
When the input amount of catalyst was 1.0 mg, toluene conversion was 7.49 %, and selectivity is 49.64 %, catalyst turn over number 10.22 * 10
4
Embodiment 4
The method for using of grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) cobalt porphyrin catalyst: have the catalyst of 1.5 mg four (4-carboxyl phenyl) cobalt porphyrin to throw in 500 ml autoclaves grafting of zinc oxide ionic bond and coordination load, add 200 ml toluene.Reaction temperature is 180 ℃, and oxygen pressure is controlled to be 0.6 MPa, and speed of agitator is controlled at 200 rev/mins, and oxygen flow is controlled to be 0.04 m
3/ h, the reaction time is at 3.5 h.The conversion ratio of toluene is 7.77 %, and the aldehyde alcohol selectivity is 49.02 %, and the catalyst turn over number is 7.21 * 10
4
Catalyst recovery is reused 10 times, and its toluene average conversion is 6.83 %, and the aldehyde alcohol average selectivity is 50.77 %, and average turn over number is 6.52 * 10
4。
When reaction temperature is 175 ℃, toluene conversion 7.18 %, selectivity 51.59 %, catalyst turn over number 6.70 * 10
4
When reaction temperature is 185 ℃, toluene conversion 9.90 %, selectivity 38.73 %, catalyst turn over number 9.16 * 10
4
Embodiment 5
1, the method step of preparation zinc oxide ionic bond grafting and coordination load four (4-carboxyl phenyl) manganoporphyrin catalyst is with embodiment 1.
2, the method for using of grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) phenyl manganoporphyrin catalyst: have the catalyst of 1.0 mg four (4-carboxyl phenyl) cobalt porphyrin to throw in 500 ml autoclaves grafting of zinc oxide ionic bond and coordination load, add 200 ml toluene.Reaction temperature is 180 ℃, and oxygen pressure is controlled to be 0.5 MPa, and speed of agitator is controlled at 200 rev/mins, and oxygen flow is controlled to be 0.04 m
3/ h, the reaction time is at 3.5 h.Toluene conversion is 7.78 %, and the aldehyde alcohol selectivity is 52.71 %, catalyst turn over number 10.74 * 10
4
When reaction temperature is 175 ℃, toluene conversion 7.51 %, aldehyde alcohol selectivity 55.18 %, turn over number 10.14 * 10
4
When reaction temperature is 185 ℃, toluene conversion 7.38 %, aldehyde alcohol selectivity 47.92 %, turn over number 10.05 * 10
4
Embodiment 6
The method for using of grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) phenyl manganoporphyrin catalyst: have the catalyst of 1.0 mg four (4-carboxyl phenyl) cobalt porphyrin to throw in 500 ml autoclaves grafting of zinc oxide ionic bond and coordination load, add 200 ml toluene.Reaction temperature is 180 ℃, and oxygen pressure is controlled to be 0.6 MPa, and speed of agitator is controlled at 200 rev/mins, and oxygen flow is controlled to be 0.04 m
3/ h, the reaction time is at 3.5 h.Toluene conversion is 8.07 %, and the aldehyde alcohol selectivity is 49.96 %, catalyst turn over number 11.24 * 10
4
When reaction pressure is 0.4MPa, toluene conversion 6.36 %, aldehyde alcohol selectivity 56.59 %, turn over number 8.74 * 10
4
Embodiment 7
The method for using of grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) phenyl manganoporphyrin catalyst: have the catalyst of 1.5 mg four (4-carboxyl phenyl) cobalt porphyrin to throw in 500 ml autoclaves grafting of zinc oxide ionic bond and coordination load, add 200 ml toluene.Reaction temperature is 180 ℃, and oxygen pressure is controlled to be 0.5 MPa, and speed of agitator is controlled at 200 rev/mins, and oxygen flow is controlled to be 0.04 m
3/ h, the reaction time is at 3.5 h.Toluene conversion is 8.19 %, and the aldehyde alcohol selectivity is 56.97 %, catalyst turn over number 7.52 * 10
4Catalyst recovery is reused 10 times, and its toluene average conversion is 7.50 %, and the aldehyde alcohol average selectivity is 51.10 %, and average turn over number is 7.27 * 10
4
When the amount that drops into catalyst is 0.5 mg, toluene conversion 5.66 %, aldehyde alcohol selectivity 53.00 %, turn over number 7.78 * 10
4
When the amount that drops into catalyst is 2.0 mg, toluene conversion 6.45 %, aldehyde alcohol selectivity 57.13 %, turn over number 4.51 * 10
4
Embodiment 8
1, the method for preparing grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) ferriporphyrin catalyst is with embodiment 1.
2, the method for using of grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) phenyl ferriporphyrin catalyst: have the catalyst of 1.5 mg four (4-carboxyl phenyl) cobalt porphyrin to throw in 500 ml autoclaves grafting of zinc oxide ionic bond and coordination load, add 200 ml toluene.Reaction temperature is 185 ℃, and oxygen pressure is controlled to be 0.6 MPa, and speed of agitator is controlled at 200 rev/mins, and oxygen flow is controlled to be 0.04 m
3/ h, the reaction time is at 4 h.Toluene conversion is 9.94 %, and the aldehyde alcohol selectivity is 43.79 %, and the catalyst turn over number is 8.97 * 10
4
Catalyst recovery repeats 10 times, and its toluene average conversion is 7.72 %, and the aldehyde alcohol average selectivity is 50.66 %, and the average turn over number of catalyst is 7.01 * 10
4
When reaction temperature is 180 ℃, toluene conversion 6.24 %, aldehyde alcohol selectivity 54.15 %, turn over number 5.69 * 10
4
When reaction temperature is 190 ℃, toluene conversion 7.26 %, aldehyde alcohol selectivity 50.81 %, turn over number 6.11 * 10
4
Embodiment 9
The method for using of grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) phenyl ferriporphyrin catalyst: have the catalyst of 1.5 mg four (4-carboxyl phenyl) cobalt porphyrin to throw in 500 ml autoclaves grafting of zinc oxide ionic bond and coordination load, add 200 ml toluene.Reaction temperature is 185 ℃, and oxygen pressure is controlled to be 0.7 MPa, and speed of agitator is controlled at 200 rev/mins, and oxygen flow is controlled to be 0.04 m
3/ h, the reaction time is at 4 h.Toluene conversion is 6.47 %, and the aldehyde alcohol selectivity is 56.60 %, and the catalyst turn over number is 5.66 * 10
4
When reaction pressure is 0.5MPa, toluene conversion 5.35 %, aldehyde alcohol selectivity 53.79 %, turn over number 4.75 * 10
4
Embodiment 10
The method for using of grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) phenyl ferriporphyrin catalyst: have the catalyst of 1.0 mg four (4-carboxyl phenyl) cobalt porphyrin to throw in 500 ml autoclaves grafting of zinc oxide ionic bond and coordination load, add 200 ml toluene.Reaction temperature is 185 ℃, and oxygen pressure is controlled to be 0.6 MPa, and speed of agitator is controlled at 200 rev/mins, and oxygen flow is controlled to be 0.04 m
3/ h, the reaction time is at 4 h.Toluene conversion is 5.38 %, and the aldehyde alcohol selectivity is 51.99 %, and the catalyst turn over number is 7.34 * 10
4
When the catalyst input amount is 2.0 mg, toluene conversion 7.41 %, aldehyde alcohol selectivity 50.39 %, turn over number 5.08 * 10
4
Claims (2)
1. the method for zinc oxide ionic bond grafting and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin agent, it is characterized in that: this method comprises the steps:
(1) the fresh Zn (OH) of preparation
2: take by weighing 71 g ZnSO
47H
2O is dissolved in the 300 ml deionized waters, is adjusted to pH=7.5 with the sodium hydroxide solution of 0.3 mol/L, and suction filtration obtains fresh Zn (OH)
2Sediment,
(2) with fresh Zn (OH)
2Sediment through dispersed with stirring in organic solvent; Add the organic solvent that is dissolved with four (4-carboxyl phenyl) metalloporphyrin again, keep 60～70 ℃ of temperature and stir 6～7 h fast, most of solvent is removed in decompression distillation again; Suction filtration, washing; Filter cake obtains grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin agent through 120～170 ℃ of vacuum drying 6～8h, and said organic solvent is acetone and ethanol.
2. the application of described ionic bond grafting of claim 1 and coordination load four (4-carboxyl phenyl) catalysis of metalloporphyrin agent is characterized in that:
The grafting of zinc oxide ionic bond and coordination load four (4-carboxyl phenyl) the catalysis of metalloporphyrin agent that take by weighing 0.5～2.0 mg four (4-carboxyl phenyl) metalloporphyrin equivalent are in autoclave; Add 200 ml cyclohexanes; Reaction pressure is controlled at 0.4～0.8 MPa; Temperature is controlled at 160～190 ℃, and mixing speed is controlled at 200～500 rev/mins, and gas flow is 0.04 m
3/ h, after heating arrived reaction temperature, aerating oxygen carried out catalytic oxidation 3.0～4.5 h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102921463A (en) * | 2012-10-12 | 2013-02-13 | 广西大学 | Nano zinc sulfide metalloporphyrin catalyst and preparation method and application thereof |
| CN105457682A (en) * | 2015-11-13 | 2016-04-06 | 广西大学 | Preparation method and catalytic application of lead sulfide immobilized tetra (pentafluorophenyl) metalloporphyrin |
| CN105712849A (en) * | 2014-12-04 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for preparing aromatic ketone by oxidation of aromatic hydrocarbon under catalytic action of metalloporphyrin framework catalyst |
| CN106000471A (en) * | 2016-06-03 | 2016-10-12 | 河南大学 | Zinc oxide-porphyrin core-shell nanorod composite material and preparation method thereof |
| CN115558118A (en) * | 2022-02-22 | 2023-01-03 | 中国科学院上海硅酸盐研究所 | Two-dimensional metal organic framework nanosheet with catalytic oxidation resistance and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921463A (en) * | 2012-10-12 | 2013-02-13 | 广西大学 | Nano zinc sulfide metalloporphyrin catalyst and preparation method and application thereof |
| CN102921463B (en) * | 2012-10-12 | 2015-08-05 | 广西大学 | A kind of Nano zinc sulfide metalloporphyrin catalyst and its preparation method and application |
| CN105712849A (en) * | 2014-12-04 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for preparing aromatic ketone by oxidation of aromatic hydrocarbon under catalytic action of metalloporphyrin framework catalyst |
| CN105712849B (en) * | 2014-12-04 | 2018-05-18 | 中国科学院大连化学物理研究所 | The method that metalloporphyrin frame material catalyst arene oxidizing prepares aromatic ketone |
| CN105457682A (en) * | 2015-11-13 | 2016-04-06 | 广西大学 | Preparation method and catalytic application of lead sulfide immobilized tetra (pentafluorophenyl) metalloporphyrin |
| CN105457682B (en) * | 2015-11-13 | 2018-02-13 | 广西大学 | The preparation method and applications of vulcanized lead immobilized four (pentafluorophenyl group) catalysis of metalloporphyrin agent |
| CN106000471A (en) * | 2016-06-03 | 2016-10-12 | 河南大学 | Zinc oxide-porphyrin core-shell nanorod composite material and preparation method thereof |
| CN106000471B (en) * | 2016-06-03 | 2018-05-01 | 河南大学 | A kind of zinc oxide-porphyrin core-shell nano rod composite material and preparation method thereof |
| CN115558118A (en) * | 2022-02-22 | 2023-01-03 | 中国科学院上海硅酸盐研究所 | Two-dimensional metal organic framework nanosheet with catalytic oxidation resistance and preparation method and application thereof |
| CN115558118B (en) * | 2022-02-22 | 2023-07-07 | 中国科学院上海硅酸盐研究所 | Two-dimensional metal organic framework nano sheet with catalytic oxidation resistance, and preparation method and application thereof |
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Application publication date: 20120919 |