CN108097321A - The synthetic method of graphene oxide with good electro catalytic activity-haematoporphyrin compound - Google Patents
The synthetic method of graphene oxide with good electro catalytic activity-haematoporphyrin compound Download PDFInfo
- Publication number
- CN108097321A CN108097321A CN201711421357.7A CN201711421357A CN108097321A CN 108097321 A CN108097321 A CN 108097321A CN 201711421357 A CN201711421357 A CN 201711421357A CN 108097321 A CN108097321 A CN 108097321A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- haematoporphyrin
- hemin
- compound
- catalytic activity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 11
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- KFKRXESVMDBTNQ-UHFFFAOYSA-N 3-[18-(2-carboxylatoethyl)-8,13-bis(1-hydroxyethyl)-3,7,12,17-tetramethyl-22,23-dihydroporphyrin-21,24-diium-2-yl]propanoate Chemical compound N1C2=C(C)C(C(C)O)=C1C=C(N1)C(C)=C(C(O)C)C1=CC(C(C)=C1CCC(O)=O)=NC1=CC(C(CCC(O)=O)=C1C)=NC1=C2 KFKRXESVMDBTNQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- -1 haematoporphyrin compound Chemical class 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 19
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical class ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910006124 SOCl2 Inorganic materials 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 229940025294 hemin Drugs 0.000 abstract description 21
- BTIJJDXEELBZFS-QDUVMHSLSA-K hemin Chemical compound CC1=C(CCC(O)=O)C(C=C2C(CCC(O)=O)=C(C)\C(N2[Fe](Cl)N23)=C\4)=N\C1=C/C2=C(C)C(C=C)=C3\C=C/1C(C)=C(C=C)C/4=N\1 BTIJJDXEELBZFS-QDUVMHSLSA-K 0.000 abstract description 19
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 238000001228 spectrum Methods 0.000 abstract description 10
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 238000002329 infrared spectrum Methods 0.000 abstract description 3
- 238000004847 absorption spectroscopy Methods 0.000 abstract 2
- 150000004032 porphyrins Chemical class 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 210000002659 acromion Anatomy 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention discloses the synthetic method of the graphene oxide haematoporphyrin compound with good electro catalytic activity, includes the following steps:(1) synthesis of GOCl：By graphene oxide chloride, the synthesis of (2) Hemin GO：Chloride graphene oxide is reacted with haematoporphyrin, obtains the Hemin GO compounds of covalent bonding.The Hemin GO of covalent bonding are characterized by infrared spectrum, ultraviolet-visible absorption spectroscopy, fluorescence spectrum, in infrared spectrogram, 1380cm‑1The peak at place；In ultraviolet-visible absorption spectroscopy figure, there is broad peak at 422 550nm；In fluorescence spectra, bands of a spectrum blue shift to 532nm, fluorescence intensity adds 159%, shows haematoporphyrin molecule and is bonded in the form of carboxyl with graphene oxide, forms the compound Hemin GO of covalent bonding.
Description
Technical field
The present invention relates to photoelectrocatalysimaterial material technical fields.More particularly, to a kind of with good electro catalytic activity
The synthetic method of graphene oxide-haematoporphyrin compound.
Background technology
Graphene is a kind of new carbon material, be by single layer of carbon atom it is tightly packed formed in honeycomb crystal lattice two
Crystal is tieed up, graphene is exactly mono-layer graphite piece.In graphene, C-C keys are with sp2Hydridization.Each carbon atom is except with σ keys and its
Outside his three carbon atoms are connected, the pi-electron of remaining pi-electron and other carbon atoms forms the big pi bond of delocalization, and electronics can be in this area
It is moved freely in domain, so that graphene has excellent electric conductivity.Since graphene edge and fault location have lone pair electrons,
Make graphene that there are the magnetic properties such as ferromagnetism.Due to the special construction of graphene monoatomic layer, make the theoretical specific surface of graphene
Product is up to 2630m2/g.Graphene also possesses unique optical property, single-layer graphene visible region transmitance up to 97%
More than.These characteristics make graphene in key areas such as nano-device, sensor, hydrogen storage material, composite material, field emmision materials
It has a wide range of applications.
Graphite oxide is a kind of mostly important graphite derivative.The report on graphene oxide can be traced back to earliest
Before 150 years, British scientist Brodie is handled crystalline flake graphite using potassium chlorate and nitric acid within 1859, finds to utilize strong oxygen
Graphite after agent treats includes carbon, hydrogen, oxygen, three kinds of elements, and this product for being referred to as " graphitic acid " by him can be stablized point
It dissipates in neutral and alkalescence water, this " graphitic acid " is exactly the graphene oxide described in we are present.Later by changing oxygen
The preparation condition of graphite alkene, and derived Staudenmaier methods and Hummer methods.Similar to graphite, graphite oxide is similary
For two-dimensional layered structure, graphene oxide by power stacked in multi-layers the effects that the hydrogen bond of interlayer together.But graphene oxide
Substantial amounts of oxygen-containing group is contained on surface, it is made to show stronger hydrophily and can be completely dispersed in water.At present, graphite oxide
Alkene is as a kind of important presoma for preparing graphene, and colleague is because some unique physical chemistry possessed by itself
Matter and extensive concern and the research for being subject to scientists.
Graphene oxide connects into different types of compound with metalloporphyrin covalent bond and light is being converted to solar energy
Material in terms of show remarkable performance.These performances have constructed the ideal photon and photoelectric material of graphene.It shows
The compound of porphyrin and graphene is applied in terms of photoelectronics and nonlinear optics there are many potential, such as equipped with solar energy
The mine car of battery and the treatment in terms of light power.What porphyrin and graphene were bonded with big pi bond, be a kind of ideal
Nonlinear material.Observe that porphyrin and metalloporphyrin have under visible infrared by this cooperation of porphyrin and graphene oxide
Very strong electronics conversion.Modification of their energy by changing the chemical method for coordinating metal forms ring.Metal substitute porphyrin
Porphyrin freer than metal shows better nonlinear optics relation.Therefore suitable various new metalloporphyrin and repair
The covalent porphyrin-like compound adornd can become better nonlinear optical material.
The content of the invention
It is an object of the present invention to provide a kind of graphene oxide with good electro catalytic activity-haematoporphyrin chemical combination
The synthetic method of object.
In order to achieve the above objectives, the present invention uses following technical proposals：
The synthetic method of graphene oxide-haematoporphyrin compound with good electro catalytic activity, includes the following steps：
(1) synthesis of chloride graphene oxide；
(2) synthesis of graphene oxide-haematoporphyrin.
The synthetic method of the above-mentioned graphene oxide with good electro catalytic activity/haematoporphyrin compound, the conjunction of step (1)
It is into method：
Measure 20mL thionyl chlorides SOCl2In flask, then weigh 100mg graphene oxides and be added to 20mL thionyl chlorides
SOCl2In, temperature is 70 DEG C, adds in 5mL and newly steams DMF, reaction carries out under nitrogen atmosphere, reacts 72h；Reaction terminates, and filters, and uses
Tetrahydrofuran is washed until filtrate is colourless；60-80 DEG C of vacuum drying 2-3h, obtains chloride graphene oxide.
The synthetic method of the above-mentioned graphene oxide with good electro catalytic activity/haematoporphyrin compound, the conjunction of step (2)
It is into method：
Weigh 15mg chlorides graphene oxide and 30mg haematoporphyrin, sample be placed in flask, add in 3mL triethylamines and
10mL steam again after DMF, under blanket of nitrogen, 80 DEG C of reaction 72h；Reaction terminates, and measures 100mL ether and is added in reaction solution, sinks
It forms sediment, filters, solid is washed with tetrahydrofuran until filtrate is colourless, and obtained solid is dried in vacuo 3h at 60-80 DEG C, obtains oxygen
Graphite alkene-haematoporphyrin.
Beneficial effects of the present invention are as follows：
(1) using the method for the present invention, the Hemin-GO of covalent bond has been synthesized, and has been inhaled by infrared spectrum, ultraviolet-visible
Receive spectrum, fluorescence spectrum is characterized.
(2) in infrared spectrogram, 1380cm-1Locate the peak occurred；In UV-visible absorption spectrum, at 422-550nm
There is broad peak；In fluorescence spectra, bands of a spectrum blue shift to 532nm, fluorescence intensity adds 159%, all shows haematoporphyrin molecule
It is bonded in the form of carboxyl with graphene oxide, forms the compound Hemin-GO of covalent bonding.
(3) explore the covalent compound of new graphene oxide and haematoporphyrin compound body and graphene oxide with
The synthesis of metal porphyrins.
Description of the drawings
The specific embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the synthetic route chart of Hemin-GO；
Fig. 2 is the infrared spectrogram of GO, GOCl, Hemin and Hemin-GO；
Fig. 3 is the uv-visible absorption spectra of GO, GOCl, Hemin and Hemin-GO；
Fig. 4 is the fluorescence spectrum of GO, GOCl, Hemin and Hemin-GO.
Wherein, GO represents graphene oxide, GOCl represents chloride graphene oxide, Hemin represents haematoporphyrin, Hemin-
GO represents graphene oxide-haematoporphyrin.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar component is indicated with identical reference numeral in attached drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
In the present invention：GO represents graphene oxide, GOCl represents chloride graphene oxide, Hemin represents haematoporphyrin,
Hemin-GO represents graphene oxide-haematoporphyrin.
1. the synthetic method of graphene oxide-haematoporphyrin compound, step are as follows：
(1) synthesis of GOCl
Measure 20mL thionyl chlorides SOCl2In flask, then weigh 100mg GO and be added to 20mL thionyl chlorides SOCl2In,
Temperature is 70 DEG C, adds in 5mL and newly steams dimethylformamide DMF, reaction carries out under nitrogen atmosphere, reacts 72h；Reaction terminates, mistake
Filter, is washed with tetrahydrofuran until filtrate is colourless；60-80 DEG C of vacuum drying 2-3h, obtains GOCl.
(2) synthesis of Hemin-GO.
15mg GOCl and 30mg haematoporphyrin Hemin are weighed, sample is placed in flask, add in 3mL triethylamines and 10mL weights
Dimethylformamide DMF after steaming, under blanket of nitrogen, 80 DEG C of reaction 72h；Reaction terminates, and measures 100mL ether and is added to reaction solution
In, precipitation filters, and solid is washed with tetrahydrofuran until filtrate is colourless, and obtained solid is dried in vacuo 3h at 60-80 DEG C, obtains
To GO-Hemin.
2. material characterization
(1) infrared spectrum
Fig. 2 is the infrared spectrogram of GO, GOCl, Hemin and Hemin-GO.As seen from the figure, graphene oxide is most strong
Strong absworption peak is in 3413cm-1(O-H stretching vibration peaks), 1618cm-1And 1384cm-1Occurs the carbonyl vibration of carboxylic acid respectively
The characteristic peak at peak and phenyl ring.GOCl is in 1616cm-1There is the stretching vibration peak of C=O in acyl chlorides, compared in GO, due to chlorine
Atom forms the conjugation for drawing electronics with carbonyl, its vibration peak is caused to be moved to high wave number.As GOCl and Hemin covalent bondings
Afterwards, 1732cm-1Not only there is the stretching vibration peak of C=O, but also in 1710cm-1There is acromion, this acromion is porphyrin
Characteristic absorption peak., may be few due to the Hemin compound molecules of bonding in Hemin-GO, it is caused to absorb vibration peak intensity
It is weaker.About in 2900cm-1The peak for occurring vibrating is to belong to aromatic C-H in GO.In 1582cm-1There is a new height in place
Peak, this is the vibration of C=C in porphyrin, and in 1108cm-1The peak for a C-O vibration occur and generating.1707cm-1Occur
Curved peak is that the C=N on haematoporphyrin ring vibrates generation.In 1380cm-1The peak that place disappears clearly shows blood porphin
Quinoline and graphene oxide compound are shown haematoporphyrin molecule and are bonded in the form of carboxyl with graphene oxide.
(2) uv-visible absorption spectra
It is the uv-visible absorption spectra of GO, GOCl, Hemin and Hemin-GO in DMF solvent by Fig. 3.Before compound,
The maximum absorption band that graphene oxide shows generates GOCl, maximum is inhaled at 268nm after GO and thionyl chloride reaction
Receipts do not change.The most strong absworption peak of free haematoporphyrin about has a wide absorption band in 400nm at 590nm.When
After GOCl bondings Hemin, most strong absworption peak is in 422nm, the 2nm compared with bands of a spectrum red shift before bonding, and compound
There is broad peak in 422-550nm, and the variation of bands of a spectrum is after being bonded bonding with haematoporphyrin due to graphene molecules, to add molecule and be total to
Drop, result in composite material and occur the phenomenon that broad peak at 422-550nm, this phenomenon can preferably illustrate Porphyrin Molecule and
Graphene oxide is effectively bonded.
(3) fluorescence spectrum
Fig. 4 is the fluorescence spectra of GO, GOCl, Hemin and Hemin-GO in DMF solvent.GO and GOCl excitation wavelengths
For 260nm, GO emission bands center is in 430nm, and after GOCl is formed, blue shift occurs for bands of a spectrum bands of a spectrum, and goes out at 310nm
The bands of a spectrum of an existing point.This is because in GO molecules-COOH group reaction after, after the hydroxyl in carboxyl is substituted by chlorine, chlorine atom
The ability of electron is less than hydroxyl, so as to reduce the conjugation of this molecule, causes emission band blue shift.GOCl further with blood
After porphyrin Hemin reactions, the compound Hemin-GO of covalent bond sum is formed, Hemin of the bands of a spectrum compared with no bonding occurs
(excitation wavelength 450nm) bands of a spectrum add 159% from 520nm blue shift to 532nm, and from the fluorescence intensity of same concentration, this
Show that molecular conjugation system significantly increases after Porphyrin Molecule Hemin is bonded with GO, and its porphyrin makes its fluorescence as donor
Intensity significantly increases.The above results fully show that Hemin molecules are bonded well with GO, form the compound of covalent bonding
Hemin-GO。
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention for those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is every to belong to this hair
The obvious changes or variations that bright technical solution is extended out is still in the row of protection scope of the present invention.
Claims (3)
1. the synthetic method of graphene oxide-haematoporphyrin compound with good electro catalytic activity, which is characterized in that including such as
Lower step：
(1) synthesis of chloride graphene oxide；
(2) synthesis of graphene oxide-haematoporphyrin.
2. the synthesis side of the graphene oxide with good electro catalytic activity/haematoporphyrin compound according to claim 1
Method, which is characterized in that the synthetic method of step (1) is：
Measure 20mL thionyl chlorides SOCl2In flask, then weigh 100mg graphene oxides and be added to 20mL thionyl chlorides SOCl2
In, temperature is 70 DEG C, adds in 5mL and newly steams DMF, reaction carries out under nitrogen atmosphere, reacts 72h；Reaction terminates, and tetrahydrochysene is used in filtering
Furans is washed until filtrate is colourless；60-80 DEG C of vacuum drying 2-3h, obtains chloride graphene oxide.
3. the synthesis side of the graphene oxide with good electro catalytic activity/haematoporphyrin compound according to claim 1
Method, which is characterized in that the synthetic method of step (2) is：
15mg chlorides graphene oxide and 30mg haematoporphyrin are weighed, sample is placed in flask, adds in 3mL triethylamines and 10mL
DMF steam again after, under blanket of nitrogen, 80 DEG C of reaction 72h；Reaction terminates, and measures 100mL ether and is added in reaction solution, precipitate, takes out
Filter, solid are washed with tetrahydrofuran until filtrate is colourless, and obtained solid is dried in vacuo 3h at 60-80 DEG C, obtain oxidation stone
Black alkene-haematoporphyrin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711421357.7A CN108097321A (en) | 2017-12-25 | 2017-12-25 | The synthetic method of graphene oxide with good electro catalytic activity-haematoporphyrin compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711421357.7A CN108097321A (en) | 2017-12-25 | 2017-12-25 | The synthetic method of graphene oxide with good electro catalytic activity-haematoporphyrin compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108097321A true CN108097321A (en) | 2018-06-01 |
Family
ID=62212789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711421357.7A Pending CN108097321A (en) | 2017-12-25 | 2017-12-25 | The synthetic method of graphene oxide with good electro catalytic activity-haematoporphyrin compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108097321A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845112A (en) * | 2021-09-22 | 2021-12-28 | 同济大学 | Porphyrin edge modified graphene oxide nano hybrid material and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103818898A (en) * | 2014-01-21 | 2014-05-28 | 东南大学 | Graphene hybrid material with controllable appearance and preparation and appearance control method thereof |
| CN103852505A (en) * | 2014-03-28 | 2014-06-11 | 哈尔滨工业大学 | Manufacturing method of graphene-porphyrin modified electrode and application of electrode |
| CN104741619A (en) * | 2015-03-11 | 2015-07-01 | 盐城工学院 | Preparation method of graphene/ferriporphyrin/gold nanoparticle composite material |
-
2017
- 2017-12-25 CN CN201711421357.7A patent/CN108097321A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103818898A (en) * | 2014-01-21 | 2014-05-28 | 东南大学 | Graphene hybrid material with controllable appearance and preparation and appearance control method thereof |
| CN103852505A (en) * | 2014-03-28 | 2014-06-11 | 哈尔滨工业大学 | Manufacturing method of graphene-porphyrin modified electrode and application of electrode |
| CN104741619A (en) * | 2015-03-11 | 2015-07-01 | 盐城工学院 | Preparation method of graphene/ferriporphyrin/gold nanoparticle composite material |
Non-Patent Citations (4)
| Title |
|---|
| HAO LIN ZOU ET AL.: "A novel electrochemical biosensor based on hemin functionalized graphene oxide sheets for simultaneous determination of ascorbic acid, dopamine and uric acid", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| M. BALA MURALI KRISHNA ET AL.: "Synthesis and structural, spectroscopic and nonlinear optical measurements of graphene oxide and its composites with metal and metal free porphyrins", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| N. GRINCEVICIUTE ET AL.: "Functional two-dimensional nanoarchitectures based on chemically converted graphene oxide and hematoporphyrin under the sulfuric acid treatment", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 段行信编: "《实用精细有机合成手册》", 31 January 2000, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845112A (en) * | 2021-09-22 | 2021-12-28 | 同济大学 | Porphyrin edge modified graphene oxide nano hybrid material and preparation and application thereof |
| CN113845112B (en) * | 2021-09-22 | 2023-06-02 | 同济大学 | Porphyrin edge-modified graphene oxide nano hybrid material and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Djire et al. | Electrocatalytic and optoelectronic characteristics of the two-dimensional titanium nitride Ti4N3Tx MXene | |
| Zhang et al. | Plasmonic Cu nanoparticle on reduced graphene oxide nanosheet support: An efficient photocatalyst for improvement of near-infrared photocatalytic H2 evolution | |
| Zhang et al. | Heterostructured d‐Ti3C2/TiO2/g‐C3N4 nanocomposites with enhanced visible‐light photocatalytic hydrogen production activity | |
| Lin et al. | Crystalline carbon nitride semiconductors prepared at different temperatures for photocatalytic hydrogen production | |
| Liu et al. | In situ bond modulation of graphitic carbon nitride to construct p–n homojunctions for enhanced photocatalytic hydrogen production | |
| Zhu et al. | Bifunctional fluorescent carbon nanodots: green synthesis via soy milk and application as metal-free electrocatalysts for oxygen reduction | |
| Liu et al. | N-doped carbon dots decorated 3D g-C3N4 for visible-light driven peroxydisulfate activation: Insights of non-radical route induced by Na+ doping | |
| He et al. | Efficient dye-sensitized solar cells from polyaniline–single wall carbon nanotube complex counter electrodes | |
| Cao et al. | Synergistic photocatalytic performance of cobalt tetra (2-hydroxymethyl-1, 4-dithiin) porphyrazine loaded on zinc oxide nanoparticles | |
| Dong et al. | Photoelectrocatalytic CO2 reduction based on metalloporphyrin-modified TiO2 photocathode | |
| Arellano et al. | Charge stabilizing tris (triphenylamine)-zinc porphyrin–carbon nanotube hybrids: synthesis, characterization and excited state charge transfer studies | |
| Ouedraogo et al. | Copper octacarboxyphthalocyanine as sensitizer of graphitic carbon nitride for efficient dye degradation under visible light irradiation | |
| Sun et al. | Synthesis and electrochemistry of β-pyrrole nitro-substituted cobalt (ii) porphyrins. The effect of the NO 2 group on redox potentials, the electron transfer mechanism and catalytic reduction of molecular oxygen in acidic media | |
| Rawling et al. | Ruthenium phthalocyanine-bipyridyl dyads as sensitizers for dye-sensitized solar cells: dye coverage versus molecular efficiency | |
| Xiao et al. | A stable and efficient photocatalytic hydrogen evolution system based on covalently linked silicon-phthalocyanine-graphene with surfactant | |
| Hijazi et al. | Formation of linear and hyperbranched porphyrin polymers on carbon nanotubes via a CuAAC “grafting from” approach | |
| Wang et al. | Boosted charge transfer in porphyrin and zinc phthalocyanine co-functionalized graphene oxide nanohybrids toward improved optical limiting and H2 evolution | |
| Pan et al. | Metal-free SiOC/g-C3N4 heterojunction composites with efficient visible-light photocatalytic H2 production | |
| Lipińska et al. | Photoactive Zn (II) Porphyrin–multi-walled carbon nanotubes nanohybrids through covalent β-linkages | |
| Singh et al. | Unravelling the structural‐property relations of porphyrinoids with respect to photo‐and electro‐chemical activities | |
| Lu et al. | Preparation and third order nonlinear optical properties of corrole functionalized GO nanohybrids | |
| CN108097321A (en) | The synthetic method of graphene oxide with good electro catalytic activity-haematoporphyrin compound | |
| Mchiri et al. | Insights into the new cadmium (II) metalloporphyrin: Synthesis, X-ray crystal structure, Hirshfeld surface analysis, photophysical and cyclic voltammetry characterization of the (morpholine){(meso-tetra (para-chloro-phenyl) porphyrinato} cadmium (II) | |
| Amini et al. | Cobalt-doped g-C3N4/MOF heterojunction composite with tunable band structures for photocatalysis aerobic oxidation of benzyl alcohol | |
| Wu et al. | Ruthenium–bipyridine complexes bearing fullerene or carbon nanotubes: synthesis and impact of different carbon-based ligands on the resulting products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180601 |