CN108097318A - Graphene oxide immobilized four（4- hydroxy phenyls）The preparation method and catalytic applications of manganoporphyrin catalysis material - Google Patents
Graphene oxide immobilized four（4- hydroxy phenyls）The preparation method and catalytic applications of manganoporphyrin catalysis material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 93
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 65
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 84
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 74
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001301 oxygen Substances 0.000 claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 21
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 230000006837 decompression Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- 238000002525 ultrasonication Methods 0.000 claims description 5
- 238000004383 yellowing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 claims 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- -1 alcohol ketone Chemical class 0.000 abstract description 6
- 239000011664 nicotinic acid Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 21
- 230000007306 turnover Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 102000002004 Cytochrome P-450 Enzyme System Human genes 0.000 description 1
- 108010015742 Cytochrome P-450 Enzyme System Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
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Abstract
A kind of preparation method and catalytic applications of graphene oxide immobilized four (4 hydroxy phenyl) manganoporphyrin catalysis material, are made of following steps：First graphite oxide is prepared with improved He Mosi methods, fluffy graphene oxide is made in graphite oxide microwave heating, it is then added in four (4 hydroxy phenyl) the manganoporphyrin solution dissolved with N.N dimethylformamides, ultrasonic 6 hours under room temperature, decompression filters, collect filter cake, and by its 60 DEG C it is dry 48 it is small when to get to required catalysis material.The catalysis material is applied to oxygen catalytic oxidation ethylbenzene and generates 1 benzyl carbinol of acetophenone and DL, and in the case where not adding the reaction condition of any solvent and any reducing agent, for conversion ratio up to 62.7%, the yield of alcohol ketone is 42.0%.In addition, the catalyst can also reuse Xun Huan catalysis 5 times, and good catalytic effect is still shown, there is actual application value, be a kind of comparatively ideal bionic catalyst.
Description
Technical field
The invention belongs to catalysis material technical fields, are specifically a kind of graphene oxide immobilized four (4- hydroxy phenyls) manganese porphin
The preparation method and catalytic applications of quinoline catalysis material.
Background technology
Ethylbenzene oxidation primary product is acetophenone and DL-1- benzyl carbinols.Acetophenone is important industrial chemicals, is to synthesize other
The intermediate of fragrance, available for essence, solvent and plastic plasticizer, it can also be used to medicine production.It is industrial that acetophenone can now
To be obtained by the byproduct of cumene oxidation phenol and acetone, it can also be closed with benzene and chloroacetic chloride in the presence of ferric trichloride
Into, but this method can generate strong acid, and corrosion can be generated to production equipment, while can cause harmful effect to environment.DL-1- benzene second
Alcohol is applied to daily use chemicals and food flavor organic synthesis, may be made as the ester perfumes such as acetic acid esters, propionic ester.Industrial oxidation at this stage
Ethylbenzene is not only of high cost, high energy consumption, but also the yield of alcohol ketone is relatively low, and selectivity is not high, thus works out at low cost, alcohol ketone yield
High, environmental-friendly catalysis material is the important directions of ethylbenzene oxidation catalysis industry.
Bionic catalyst catalytic oxidation is research direction popular in the main method that current ethylbenzene is catalyzed, because metal
Porphyrin is a kind of important bionic catalyst, high efficiency, height can be embodied in catalysis with activate molecular oxygen in a mild condition
The advantages of selective and environmental-friendly, for metalloporphyrin bionic catalyst there is also problems with, metalloporphyrin stability is bad, matches somebody with somebody
Body prepares of high cost, and catalytic efficiency is not high, and easy dimerization loses catalytic activity in reaction, it is difficult to recycle and reuse.By metal
Porphyrin is immobilized can effectively to solve the above problems in insoluble carrier formation heterogeneous system, can improve the steady of metalloporphyrin
Qualitative and catalytic activity, and the number of its reuse can be increased.It, can be immobilized in oxidation stone by metalloporphyrin based on the principle
On black this insoluble carrier of alkene, meanwhile, good electrochemistry, mechanics and the optical property that graphene oxide possesses pass through
Microwave radiation technology prepares the graphene oxide composite material of certain specific surface area, and metalloporphyrin can be overcome many scarce in catalysis oxidation
Point provides the broader visual field and direction with a greater variety for metalloporphyrin study on the carrier.
The content of the invention
The present invention is inefficient in order to overcome current Ethylbenzene Catalytic Oxidation, and catalysis of metalloporphyrin efficiency is low and recycles not
Just problems provide the preparation method of a kind of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material and urge
Change application.Not only metalloporphyrin dosage is few for graphene oxide immobilized four (4- hydroxy phenyls) the manganoporphyrin catalysis material being prepared into,
It can reuse often, and after multiplicating, still show good catalytic effect.
The present invention is to be achieved through the following technical solutions object above：A kind of graphene oxide immobilized four (4- hydroxy phenyls)
Manganoporphyrin catalysis material is made of the raw material of following parts by weight：200~300 parts of the concentrated sulfuric acid, 8~12 parts of graphite powder, sodium nitrate 4
~6 parts, 30~45 parts of potassium permanganate, 1000~1500 parts of distilled water, 150~250 parts of 5% hydrogen peroxide, 5% hydrochloric acid 1000~
1500 parts, four 0.010~0.014 part of (4- hydroxy phenyls) manganoporphyrins, 5~8 parts of N.N- dimethylformamides.
The preparation method of graphene oxide immobilized four (4- hydroxy phenyls) the manganoporphyrin catalysis material, by following steps group
Into：
(1) graphite oxide is prepared：200~300 parts of concentrated sulfuric acids are added in three-neck flask, is placed in cold-trap and is kept for five points
Clock adds 8~12 parts of graphite powders and 4~6 parts of sodium nitrate, is allowed to be slowly added to potassium permanganate 30~45 after reacting 30 minutes
Part, reaction 1 it is small when after, take out, treat room temperature, the reaction was continued under 35 DEG C of water-baths 1 it is small when after add in 500~750 parts of distilled water,
Continue to be slowly added to 150~250 part of 5% hydrogen peroxide until liquid whole yellowing, it is clear to remove upper strata for stratification
Liquid, with 1000~1500 part 10% of salt acid elution repeatedly to can't detect sulfate ion, to get oxygen when 60 DEG C of dryings 48 are small
Graphite；
(2) graphene oxide is prepared：6~8 parts of graphite oxides is taken to be placed in microwave and act on 5 minutes to get graphene oxide,
It is spare；
(3) graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin is prepared：5~7 parts of steps are added in round-bottomed flask
(2) graphene oxide being prepared into is scattered in 500~750 parts of distilled water, by 0.010~0.014 part four (4- hydroxy phenyls)
Manganoporphyrin is dissolved in 5~8 parts of N.N- dimethylformamides, is subsequently poured into the dispersion liquid of graphene oxide, and ultrasonication 6 is small
When, decompression filters to obtain filter cake, by filter cake be placed at 60 DEG C dry 48 it is small when to get to 5~7 parts of graphene oxides immobilized 0.010
The catalysis material of~0.014 part of four (4- hydroxy phenyls) manganoporphyrin.
Described four (4- hydroxy phenyls) manganoporphyrin structure is (I), and graphene oxide structure is (II), and graphene oxide is immobilized
The structural formula of four (4- hydroxy phenyls) manganoporphyrin catalysis materials is (III)：
(4- hydroxy phenyls) the manganoporphyrin catalysis material of graphene oxide immobilized four is generated in oxygen catalytic oxidation ethylbenzene
Application in acetophenone and DL-1- benzyl carbinols.
(4- hydroxy phenyls) the manganoporphyrin catalysis material of graphene oxide immobilized four is generated in oxygen catalytic oxidation ethylbenzene
Application in acetophenone and DL-1- benzyl carbinols weighs the graphene oxide containing 0.25~1mg tetra- (4- hydroxy phenyls) manganoporphyrin
Immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material is put into autoclave, adds 200mL ethylbenzene, and mixing speed control exists
200~250r/min, is passed through oxygen when being warming up to 160~190 DEG C, pressure is controlled in 0.5~0.8MPa, oxygen flow 0.02
~0.03m3/ h, reaction time 4.0h.
Compared with prior art, the advantageous effect that the present invention obtains is：
1st, catalysis material, graphene oxide and four (4- are prepared with graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin
Hydroxy phenyl) manganoporphyrin forms composite material, and which simulates cytochrome P-450 enzyme system well, and by means of
The excellent structure of graphene oxide so that the material is more easy to recycle, and improves the catalytic performance of catalyst, and environmental protection easily recycling
It utilizes, greatly reduces catalysis cost.
2nd, graphene oxide has larger specific surface area, good nano aperture and a thermal stability, metalloporphyrin by π-
π non-covalent bond effects accumulate surface of graphene oxide, in addition graphene oxide pi bond electrons and four (4- hydroxy phenyls) manganoporphyrins
Manganese ion interaction, while four (4- hydroxy phenyls) hydroxyls of manganoporphyrin and the hydroxyl of graphene oxide and carboxyl form hydrogen
Key, reason, graphene oxide and four (4- hydroxy phenyls) manganoporphyrins interact to form graphene oxide immobilized four in summary
(4- hydroxy phenyls) manganoporphyrin catalysis material.
3rd, when the catalysis material prepared is applied to oxygen catalytic oxidation ethylbenzene generation acetophenone and DL-1- benzyl carbinols, turn
For rate up to 62.7%, the yield of alcohol ketone is 42.0%.
4th, catalysis material preparation method is simple, at low cost, and energy consumption is few, and without adding in solvent, reaction condition is relatively mild, energy
Suitable for various reaction units, it is easy to separate from product.
5th, graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material provided, can recycle reuse,
Recycling catalysis 5 times, still shows good catalytic effect.Metalloporphyrin dosage is few, is easily recycled, and has actual
Application value is a kind of ideal bionic catalyst.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 5um.
Specific embodiment
Below in conjunction with the preparation of specific embodiment immobilized to graphene oxide four (4- hydroxy phenyls) manganoporphyrin catalysis material
Methods and applications further illustrate, but are not limited to protection scope of the present invention.
First, the preparation of four immobilized (4- hydroxy phenyls) manganoporphyrin catalysis materials of graphene oxide
Prepare embodiment 1
The preparation method of graphene oxide immobilized four (4- hydroxy phenyls) the manganoporphyrin catalysis material, by following steps group
Into：
(1) graphite oxide is prepared：200 parts of concentrated sulfuric acids are added in three-neck flask, is placed in cold-trap and is kept for five minutes, then
Add in 8 parts of graphite powders and 4 parts of sodium nitrate, be allowed to be slowly added to 30 parts of potassium permanganate after reacting 30 minutes, when reaction 1 is small after,
Take out, treat room temperature, the reaction was continued under 35 DEG C of water-baths 1 it is small when after add in 500 parts of distilled water, continue to be slowly added to 150 parts 5% pair
Oxygen water is until liquid whole yellowing, stratification, removes supernatant liquor, multiple with 1000 part 5% of salt acid elution
To can't detect sulfate ion, to get graphite oxide when 60 DEG C of dryings 48 are small；
(2) graphene oxide is prepared：6 parts of graphite oxides is taken to be placed in microwave to act on 5 minutes, graphene oxide is made, it is standby
With；
(3) graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin is prepared：5 parts of steps (2) are added in round-bottomed flask
Graphene oxide obtained is dispersed in 500 parts of distilled water, and 0.010 part of four (4- hydroxy phenyls) manganoporphyrin is dissolved in 5 parts
In N.N- dimethylformamides, it is subsequently poured into the dispersion liquid of graphene oxide, when ultrasonication 6 is small, decompression filters to obtain filter cake,
By filter cake be placed at 60 DEG C dry 48 it is small when to get to immobilized 0.010 part four (4- hydroxy phenyls) manganoporphyrin of 5 parts of graphene oxides
Catalysis material.
Prepare embodiment 2
The preparation method of graphene oxide immobilized four (4- hydroxy phenyls) the manganoporphyrin catalysis material, by following steps group
Into：
(1) graphite oxide is prepared：250 parts of concentrated sulfuric acids are added in three-neck flask, is placed in cold-trap and is kept for five minutes, then
Add in 10 parts of graphite powders and 5 parts of sodium nitrate, be allowed to be slowly added to 38 parts of potassium permanganate after reacting 30 minutes, when reaction 1 is small after,
Take out, treat room temperature, the reaction was continued under 35 DEG C of water-baths 1 it is small when after add in 625 distilled water, continue to be slowly added to 200 part of 5% dioxygen
Water is until liquid whole yellowing, stratification, removes supernatant liquor, with 1250 part 5% of salt acid elution repeatedly extremely
Sulfate ion is can't detect, to get graphite oxide when 60 DEG C of dryings 48 are small；
(2) graphene oxide is prepared：7 parts of graphite oxides is taken to be placed in microwave to act on 5 minutes, graphene oxide is made, it is standby
With；
(3) graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin is prepared：6 parts of steps (2) are added in round-bottomed flask
Graphene oxide obtained is dispersed in 625 parts of distilled water, and 0.012 part of four (4- hydroxy phenyls) manganoporphyrin is dissolved in 6.5 parts
In N.N- dimethylformamides, it is subsequently poured into the dispersion liquid of graphene oxide, when ultrasonication 6 is small, decompression filters to obtain filter cake,
By filter cake be placed at 60 DEG C dry 48 it is small when to get to immobilized 0.012 part four (4- hydroxy phenyls) manganoporphyrin of 6 parts of graphene oxides
Catalysis material.
Prepare embodiment 3
The preparation method of graphene oxide immobilized four (4- hydroxy phenyls) the manganoporphyrin catalysis material, by following steps group
Into：
(1) graphite oxide is prepared：300 parts of concentrated sulfuric acids are added in three-neck flask, is placed in cold-trap and is kept for five minutes, then
Add in 12 parts of graphite powders and 6 parts of sodium nitrate, be allowed to be slowly added to 45 parts of potassium permanganate after reacting 30 minutes, when reaction 1 is small after,
Take out, treat room temperature, the reaction was continued under 35 DEG C of water-baths 1 it is small when after add in 750 parts of distilled water, continue to be slowly added to 250 parts 5% pair
Oxygen water is until liquid whole yellowing, stratification, removes supernatant liquor, multiple with 1500 part 5% of salt acid elution
To can't detect sulfate ion, to get graphite oxide when 60 DEG C of dryings 48 are small；
(2) graphene oxide is prepared：8 parts of graphite oxides is taken to be placed in microwave to act on 5 minutes, graphene oxide is made, it is standby
With；
(3) graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin is prepared：7 parts of steps (2) are added in round-bottomed flask
Graphene oxide obtained is dispersed in 750 parts of distilled water, and 0.014 part of four (4- hydroxy phenyls) manganoporphyrin is dissolved in 8 parts
In N.N- dimethylformamides, it is subsequently poured into the dispersion liquid of graphene oxide, when ultrasonication 6 is small, decompression filters to obtain filter cake,
By filter cake be placed at 60 DEG C dry 48 it is small when to get to immobilized 0.014 part four (4- hydroxy phenyls) manganoporphyrin of 7 parts of graphene oxides
Catalysis material.
Graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin scanning electron microscope detection figure that Fig. 1 is 5um, is surveyed by BET
It is 55.23m to obtain its specific surface area2/ g, pore size 16.16nm.
2nd, graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material answering in oxygen catalytic oxidation ethylbenzene
With Application Example 1
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs and prepares containing for embodiment 1
There is graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 0.5mg tetra- (4- hydroxy phenyls) manganoporphyrin, be put into
In the autoclave of 300mL, 200mL ethylbenzene is added in, controls mixing speed that it is anti-to be passed through oxygen when being warming up to 160 DEG C for 250r/min
Should, oxygen pressure 0.8MPa, oxygen flow 0.03m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
21.6%, keto-alcohol is selectively 65.8%, and catalyst turn over number is 2.4 × 105, keto-alcohol yield is 14.2%.
Application Example 2
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs and prepares containing for embodiment 1
There is graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 0.5mg tetra- (4- hydroxy phenyls) manganoporphyrin, be put into
In the autoclave of 300mL, 200mL ethylbenzene is added in, controls mixing speed that it is anti-to be passed through oxygen when being warming up to 170 DEG C for 250r/min
Should, oxygen pressure 0.8MPa, oxygen flow 0.03m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
26.1%, keto-alcohol is selectively 65.7%, and catalyst turn over number is 2.9 × 105, keto-alcohol yield is 17.1%.
Application Example 3
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs and prepares containing for embodiment 1
There is graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 0.5mg tetra- (4- hydroxy phenyls) manganoporphyrin, be put into
In the autoclave of 300mL, 200mL ethylbenzene is added in, controls mixing speed that it is anti-to be passed through oxygen when being warming up to 180 DEG C for 250r/min
Should, oxygen pressure 0.8MPa, oxygen flow 0.03m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
37.2%, keto-alcohol is selectively 65.2%, and catalyst turn over number is 4.0 × 105, keto-alcohol yield is 24.3%.
Application Example 4
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs and prepares containing for embodiment 1
There is graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 0.5mg tetra- (4- hydroxy phenyls) manganoporphyrin, be put into
In the autoclave of 300mL, 200mL ethylbenzene is added in, controls mixing speed that it is anti-to be passed through oxygen when being warming up to 190 DEG C for 250r/min
Should, oxygen pressure 0.8MPa, oxygen flow 0.03m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
54.8%, keto-alcohol is selectively 60.2%, and catalyst turn over number is 5.7 × 105, keto-alcohol yield is 33.0%.
Application Example 5
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs and prepares containing for embodiment 1
There is graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 0.5mg tetra- (4- hydroxy phenyls) manganoporphyrin, be put into
In the autoclave of 300mL, 200mL ethylbenzene is added in, controls mixing speed that it is anti-to be passed through oxygen when being warming up to 190 DEG C for 200r/min
Should, oxygen pressure 0.5MPa, oxygen flow 0.02m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
33.4%, keto-alcohol is selectively 67.5%, and catalyst turn over number is 3.7 × 105, keto-alcohol yield is 22.6%.
Application Example 6
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs and prepares containing for embodiment 1
There is graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 0.5mg tetra- (4- hydroxy phenyls) manganoporphyrin, be put into
In the autoclave of 300mL, 200mL ethylbenzene is added in, controls mixing speed that it is anti-to be passed through oxygen when being warming up to 190 DEG C for 225r/min
Should, oxygen pressure 0.6MPa, oxygen flow 0.025m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
36.3%, keto-alcohol is selectively 65.8%, and catalyst turn over number is 3.9 × 105, keto-alcohol yield is 23.9%.
Application Example 7
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs and prepares containing for embodiment 1
There is graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 0.5mg tetra- (4- hydroxy phenyls) manganoporphyrin, be put into
In the autoclave of 300mL, 200mL ethylbenzene is added in, controls mixing speed that it is anti-to be passed through oxygen when being warming up to 190 DEG C for 250r/min
Should, oxygen pressure 0.7MPa, oxygen flow 0.03m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
62.7%, keto-alcohol is selectively 66.9%, and catalyst turn over number is 6.4 × 105, keto-alcohol yield is 42.0%.
Application Example 8
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs and prepares containing for embodiment 1
There is graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 0.25mg tetra- (4- hydroxy phenyls) manganoporphyrin, be put into
In the autoclave of 300mL, 200mL ethylbenzene is added in, controls mixing speed that it is anti-to be passed through oxygen when being warming up to 190 DEG C for 250r/min
Should, oxygen pressure 0.7MPa, oxygen flow 0.03m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
59.0%, keto-alcohol is selectively 64.7%, and catalyst turn over number is 6.0 × 105, keto-alcohol yield is 38.1%.
Application Example 9
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs title and prepares Example 1
Graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material containing 0.75mg tetra- (4- hydroxy phenyls) manganoporphyrin,
It is put into the autoclave of 300mL, adds in 200mL ethylbenzene, mixing speed is controlled to be passed through oxygen when being warming up to 190 DEG C for 250r/min
Solid/liquid/gas reactions, oxygen pressure 0.7MPa, oxygen flow 0.03m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
45.0%, keto-alcohol is selectively 67.7%, and catalyst turn over number is 4.6 × 105, keto-alcohol yield is 29.1%.
Application Example 10
The application of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material：It weighs and prepares containing for embodiment 1
There is graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of 1.00mg tetra- (4- hydroxy phenyls) manganoporphyrin, be put into
In the autoclave of 300mL, 200mL ethylbenzene is added in, controls mixing speed that it is anti-to be passed through oxygen when being warming up to 190 DEG C for 250r/min
Should, oxygen pressure 0.7MPa, oxygen flow 0.03m3/ h reacts 4.0h.The conversion ratio of ethylbenzene is respectively after reaction
32.4%, keto-alcohol is selectively 68.1%, and catalyst turn over number is 3.6 × 105, keto-alcohol yield is 22.1%.
In conclusion at 190 DEG C of temperature and pressure 0.7MPa, take containing 0.5mg tetra- (4- hydroxy phenyls) manganoporphyrin
Graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material, mixing speed 250r/min, oxygen flow are
0.03m3When/h, reaction time 4.0h, the catalytic activity of this catalysis material is optimal, conversion of ethylbenzene 62.7%, alcohol ketone yield
For 42.0%.When after reaction, standing allows catalysis material and reaction mixture natural subsidence, and then its mixture is divided
From, after catalysis material natural air drying, recycle this catalysis material and be used further to oxygen catalytic oxidation ethylbenzene, reusable 5 times.
The conversion ratio of wherein ethylbenzene is respectively 62.7%, 48.5%, 51.5%, 50.5%, 48.8%；Alcohol ketone selectivity for 66.9%,
71.7%th, 68.6%, 69.8%, 69.8%；Keto-alcohol yield is 42.0%, 34.8%, 35.3%, 35.2%, 34.0%.
Claims (5)
1. a kind of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material, which is characterized in that by following parts by weight
Raw material composition：200~300 parts of the concentrated sulfuric acid, 8~12 parts of graphite powder, 4~6 parts of sodium nitrate, 30~45 parts of potassium permanganate, distillation
1000~1500 parts of water, 150~250 parts of 5% hydrogen peroxide, 1000~1500 parts of 5% hydrochloric acid, four (4- hydroxy phenyls) manganoporphyrins
0.010~0.014 part, 5~8 parts of N.N- dimethylformamides.
2. the preparation method of graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material according to claim 1,
It is characterized in that, it comprises the steps of：
(1) graphite oxide is prepared：200~300 parts of concentrated sulfuric acids are added in three-neck flask, is placed in cold-trap and is kept for five minutes,
8~12 parts of graphite powders and 4~6 parts of sodium nitrate are added, are allowed to be slowly added to 30~45 parts of potassium permanganate after reacting 30 minutes, instead
Answer 1 it is small when after, take out, treat room temperature, the reaction was continued under 35 DEG C of water-baths 1 it is small when after add in 500~750 distilled water, continue to delay
Slowly 150~250 part of 5% hydrogen peroxide is added in until liquid whole yellowing, and stratification removes supernatant liquor, uses
1000~1500 part 10% of salt acid elution is repeatedly to can't detect sulfate ion, to get oxidation stone when 60 DEG C of dryings 48 are small
Ink；
(2) graphene oxide is prepared：6~8 parts of graphite oxides is taken to be placed in microwave and act on 5 minutes to get graphene oxide, it is standby
With；
(3) graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin is prepared：5 parts of steps (2) are added in round-bottomed flask to prepare
The graphene oxide obtained is scattered in 500~750 parts of distilled water, and 0.010~0.014 part of four (4- hydroxy phenyls) manganoporphyrin is molten
Solution is subsequently poured into 5~8 parts of N.N- dimethylformamides in the dispersion liquid of graphene oxide, when ultrasonication 6 is small, decompression
Filter to obtain filter cake, by filter cake be placed at 60 DEG C dry 48 it is small when to get to 5~7 parts of graphene oxides immobilized 0.010~0.014
The catalysis material of four (4- hydroxy phenyls) manganoporphyrins of part.
3. according to 1 and 2 graphene oxide immobilized four (4- hydroxy phenyls) the manganoporphyrin catalysis material of claim, feature exists
It is (I) in, described four (4- hydroxy phenyls) manganoporphyrin structure, graphene oxide structure is (II), the immobilized four (4- of graphene oxide
Hydroxy phenyl) manganoporphyrin catalysis material structural formula be (III)：
The graphene oxide of claim 1 or 2 immobilized four 4. (4- hydroxy phenyls) manganoporphyrin catalysis material is in catalytic oxygen oxygen
Change the application in ethylbenzene generation acetophenone and DL-1- benzyl carbinols.
5. graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material is in catalytic oxygen oxygen according to claim 4
Change the application in ethylbenzene generation acetophenone and DL-1- benzyl carbinols, which is characterized in that weigh containing (the 4- hydroxy benzenes of 0.25~1mg tetra-
Base) graphene oxide immobilized four (4- hydroxy phenyls) manganoporphyrin catalysis material of manganoporphyrin is put into autoclave, add 200mL
Ethylbenzene, mixing speed control are passed through oxygen in 200~250r/min when being warming up to 160~190 DEG C, pressure control 0.5~
0.8MPa, oxygen flow are 0.02~0.03m3/ h, reaction time 4.0h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046460A (en) * | 2018-08-03 | 2018-12-21 | 湖南大学 | A kind of composite electrocatalyst for electro-catalysis reduction nitrobenzene |
| CN113025155A (en) * | 2021-02-07 | 2021-06-25 | 南京工业大学 | Preparation method of bio-based coating with high anti-corrosion property |
| CN114073983A (en) * | 2020-08-17 | 2022-02-22 | 万华化学集团股份有限公司 | Diisopropylbenzene oxidation catalyst, preparation method thereof and method for preparing diisopropylbenzene dibenzyl alcohol by using diisopropylbenzene oxidation catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554302A (en) * | 2013-10-29 | 2014-02-05 | 广西大学 | Preparation method and application for chitosan-grafted quadri(p-carboxylphenyl) metalloporphyrin |
| CN105597828A (en) * | 2015-12-28 | 2016-05-25 | 上海应用技术学院 | Method for preparing graphene oxide/porphyrin composite photocatalyst |
| CN106179502A (en) * | 2016-07-05 | 2016-12-07 | 广西大学 | The preparation method and application of graphene oxide immobilized four (4 carboxyl phenyl) manganoporphyrin catalysis material |
-
2017
- 2017-12-12 CN CN201711319177.8A patent/CN108097318A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554302A (en) * | 2013-10-29 | 2014-02-05 | 广西大学 | Preparation method and application for chitosan-grafted quadri(p-carboxylphenyl) metalloporphyrin |
| CN105597828A (en) * | 2015-12-28 | 2016-05-25 | 上海应用技术学院 | Method for preparing graphene oxide/porphyrin composite photocatalyst |
| CN106179502A (en) * | 2016-07-05 | 2016-12-07 | 广西大学 | The preparation method and application of graphene oxide immobilized four (4 carboxyl phenyl) manganoporphyrin catalysis material |
Non-Patent Citations (1)
| Title |
|---|
| RIYUE GE ET AL.: "The influence of combination mode on the structure and properties of porphyrin–graphene oxide composites", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046460A (en) * | 2018-08-03 | 2018-12-21 | 湖南大学 | A kind of composite electrocatalyst for electro-catalysis reduction nitrobenzene |
| CN114073983A (en) * | 2020-08-17 | 2022-02-22 | 万华化学集团股份有限公司 | Diisopropylbenzene oxidation catalyst, preparation method thereof and method for preparing diisopropylbenzene dibenzyl alcohol by using diisopropylbenzene oxidation catalyst |
| CN114073983B (en) * | 2020-08-17 | 2023-05-30 | 万华化学集团股份有限公司 | Diisopropylbenzene oxidation catalyst and preparation method thereof, and method for preparing diisopropylbenzene dibenzyl alcohol by using diisopropylbenzene oxidation catalyst |
| CN113025155A (en) * | 2021-02-07 | 2021-06-25 | 南京工业大学 | Preparation method of bio-based coating with high anti-corrosion property |
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