CN105688995B - A kind of method for preparing metalloporphyrin-graphene nanocomposite material at ambient temperature - Google Patents
A kind of method for preparing metalloporphyrin-graphene nanocomposite material at ambient temperature Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 24
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- -1 cationic porphyrin Chemical class 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 27
- 238000000862 absorption spectrum Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000001455 metallic ions Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 208000011580 syndromic disease Diseases 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 15
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 3
- 230000003340 mental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011282 treatment Methods 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- MRHHHYZFDDQAQL-UHFFFAOYSA-N 2,3,6,7-tetramethylquinoxaline Chemical compound CC1=C(C)N=C2C=C(C)C(C)=CC2=N1 MRHHHYZFDDQAQL-UHFFFAOYSA-N 0.000 description 29
- 101100361108 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) eas gene Proteins 0.000 description 28
- LRXUJWQJCUIVBG-UHFFFAOYSA-N 4-chloro-6-(trifluoromethyl)-2,1,3-benzothiadiazole Chemical compound C1=C(C(F)(F)F)C=C(Cl)C2=NSN=C21 LRXUJWQJCUIVBG-UHFFFAOYSA-N 0.000 description 12
- 101100449516 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) grg-1 gene Proteins 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000001338 self-assembly Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- NCAJWYASAWUEBY-UHFFFAOYSA-N 3-[20-(2-carboxyethyl)-9,14-diethyl-5,10,15,19-tetramethyl-21,22,23,24-tetraazapentacyclo[16.2.1.1^{3,6}.1^{8,11}.1^{13,16}]tetracosa-1(21),2,4,6(24),7,9,11,13,15,17,19-undecaen-4-yl]propanoic acid Chemical compound N1C2=C(C)C(CC)=C1C=C(N1)C(C)=C(CC)C1=CC(C(C)=C1CCC(O)=O)=NC1=CC(C(CCC(O)=O)=C1C)=NC1=C2 NCAJWYASAWUEBY-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- AIRPQPQNHSLMPG-UHFFFAOYSA-N 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin-2-carboxylic acid Chemical compound C(=O)(O)C1=C2NC(=C1)C(=C1C=CC(=N1)C(=C1C=CC(N1)=C(C=1C=CC(N=1)=C2C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 AIRPQPQNHSLMPG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229930003779 Vitamin B12 Natural products 0.000 description 1
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention discloses a kind of methods for preparing metalloporphyrin graphene nanocomposite material at ambient temperature.The nanocomposite is in aqueous solution using metal ion, porphyrin, graphene as primary raw material, regulate and control the ability that metal ion is embedded in porphyrin ring by changing the electronation degree of graphene oxide, the molecular structure of cationic porphyrin, system pH etc., realize the quick preparation of metalloporphyrin graphene nanocomposite material at ambient temperature.Compared with the technology of preparing of existing metalloporphyrin graphene composite material, method provided by the invention realizes the complexation process of metal ion and porphyrin without hot conditions or long-time heating reflux course, preparation condition green is mild, simple to operation, stable structure, suitable for amplification preparation and production application, had broad application prospects in fields such as catalysis material, photoelectric material and heavy mental treatments.
Description
Technical field
The present invention relates to graphene composite material preparation fields, specifically, are related to preparing metal porphin at ambient temperature
The new green method of quinoline-graphene complex.
Background technology
Graphene is the two-dimension nano materials of single layer of carbon atom composition, has high-specific surface area, high-termal conductivity and highly conductive
The excellent performances such as property.As what graphene was studied deepens continuously, people put forward higher requirements its functionalization, therefore graphite
Alkene composite material is got the attention.
Two protons are formed metalloporphyrin after being replaced by metal in porphyrin ring, by introduce different metal centers from
Substituent group on son, change porphyrin ring etc. can show diversified molecule performance, such as be widely present in the function of nature
Chlorophyll (i.e. magnesium porphyrin), ferroheme (i.e. ferriporphyrin), vitamin B12 (i.e. Cob altporphyrin) in unit etc. contain metalloporphyrin
Nuclear structure.Since the height of the good stability of metalloporphyrin is conjugated big π structures, a kind of electronics object can be used as, it can
It is assembled, is had in the fields such as catalysis material and photoelectric material tempting with carbon/silicon nano material, oxide-based nanomaterial etc.
Application prospect.
Graphene is with excellent physical and chemical performance, metalloporphyrin with good electron donation and multi-functional tuning
Ability can obtain the multifunctional graphite vinyl composite material of Novel series with reference to the characteristics of the two.Such as Bratche is at first by being esterified
Reaction is prepared for the carboxyl tetraphenylporphyrin/graphene oxide composite material being connected with covalent bond, which has good light
Absorbent properties and optical stability (Baskaran D., Mays J.W., Zhang X.P., Bratcher
M.S.J.Am.Chem.Soc,2005,127:6916–6917)；Subsequent Chen and Tagmatarchis seminar is prepared for amino
The composite material that porphyrin/graphene oxide is keyed by amide, and have studied its optical Limiting feature and its be sensitized too in fuel
Application (Xu Y.F., Liu Z.B., Chen Y.S.Adv.Mater.2009,21 in positive energy battery:1275-1279；
Karousis N.,Sandanayaka A.S.D.,Hasobe T.J Mater.Chem.2011,21:109-117)；Stone Gao Quan
With bring up Huangsong first teach successively be prepared for cationic porphyrin/redox graphene non-covalent complex, and be applied to cadmium from
Analysis detection (Xu Y.X., Zhao L., the Bai H.J.Am.Chem.Soc.2009,131 of son and chlorite:13490-
13497；Tu W.W.,Lei J P,Ju H X.Chem.Eur.J.2010,16:10771-10777)；Grinceviciute etc.
Graphene oxide/haematoporphyrin compound is applied to photodynamic therapy (Grinceviciute N., Snopok B., Snitka
V.Chem.Eng.J.,2014,225,577-584)；Zhou etc. prepares copper porphyrin/graphene complex and as ammonia gas sensor
(Zhou X Q,Wang X L,Wang B.Sensors and Actuators B:Chemical,2014,193:340-348)。
The studies above greatly enriches the preparation method and application field of porphyrin-graphene complex.
But metalloporphyrin-graphene method is prepared at present first to synthesize metalloporphyrin, then prepare metalloporphyrin-graphite
Alkene compound, and the condition for synthesizing metalloporphyrin synthesizes under high-temperature heating or for a long time harsh conditions such as reflux, so seeking
A kind of green method for fast preparing metalloporphyrin-graphene under room temperature is looked for be of great significance.
Invention content
The present invention is intended to provide the preparation method of a kind of metalloporphyrin-graphene complex, this method is at ambient temperature
Aqueous solution in using metal ion, porphyrin, graphene as primary raw material realize metalloporphyrin-graphene nanocomposite material it is fast
Prepared by speed, without being heated to reflux process.
Technical scheme is as follows：
A kind of metalloporphyrin-graphene nanocomposite material, general structure are as follows：
Wherein substituent R is CH3,CH2CH3,(CH2)2CH3,(CH2)3CH3,(CH2)4CH3,(CH2)5CH3,(CH2)3OH,
CH2COOCH2CH3,CH2C6H5,CH2C6H4CH3And CH2C6H4NO2In one kind；
Wherein M be metal ion, preferably Zn2+,Cd2+,Pb2+Or Hg2+；
Wherein graphene is the graphene oxide of gradient reduction, is hydrated by adjusting with the reducing agent of graphite oxide alkene reaction
The amount of hydrazine, which carries out gradient reduction, to be obtained.
The preparation method of above-mentioned metalloporphyrin-graphene nanocomposite material, synthetic route is as follows,
Include the following steps：
(1) serial four pyridylporphyrins are synthesized using Alder-longer methods, the alkylated reaction of N is recycled to synthesize series sun
Ion porphyrin；The commercialization of such compound, also can directly buy；
(2) graphene oxide is prepared using Hummers methods, ultrasonic disperse obtains the graphene oxide of 0.15~1.5mg/mL
Dispersion liquid, gradient restored after graphene oxide dispersion；
(3) compound concentration is 1~100 μM (i.e. 10-6~10-4Mol/L cationic porphyrin aqueous solution), thereto dropwise
The graphene oxide dispersion after reduction is added in, shakes up standing, it is multiple to monitor porphyrin-graphene by uv-visible absorption spectra
Close the generating process of object；
(4) metal ion solution is added dropwise to porphyrin-graphene complex solution again, makes the substance of compound and metal ion
Amount concentration reach 1:1~5 (complex concentration on the basis of porphyrin concentration, due to Porphyrin Molecule structure, graphene reduction journey
The difference of degree, species of metal ion, optimal concentration proportioning can also have differences), room temperature or standing is shaken up under room temperature, pass through
When uv-visible absorption spectra monitoring compound reaches stable red shift, that is, obtain metalloporphyrin-graphene nanocomposite material.
Further, in preparation process (2), gradient reduction is specially：With 40mL, 0.15mg/mL graphite oxides
On the basis of alkene dispersion liquid, 80% hydrazine hydrate solution of 0-10 μ L, the graphene oxide dispersion after being restored are added dropwise thereto.
Further, the metal ion is preferably Zn2+,Cd2+,Pb2+Or Hg2+。
Further, in preparation process (3), the porphyrin concentration of aqueous solution minimum 10 of preparation-6Mol/L, by it is ultraviolet-can
The generating process of porphyrin-graphene complex can be monitored by seeing the characteristic peak of absorption spectrum mesoporphyrin.
In preparation process (4), the preparation of uv-visible absorption spectra monitoring metalloporphyrin-graphene complex is utilized
Journey, it is simple and practicable, it can carry out at ambient temperature.
Compared with prior art, the beneficial effects of the present invention are：
The present invention without preparing metalloporphyrin under severe conditions, and preparation process is quick, and preparation condition is mild, to prepare gold
Belong to porphyrin-graphene complex and provide a kind of new green method.In addition, the electronation journey by changing graphene oxide
Degree, the molecular structure of cationic porphyrin, system pH etc. come regulate and control metal ion insertion porphyrin ring ability, prepared nanometer
Compound is a kind of green wood for having important application value in fields such as catalysis material, photoelectric material and heavy mental treatments
Material.
Description of the drawings
Fig. 1 is to titrate 1 μM of bromination four of 3mL (N- pyridylpropyls) porphyrin using the graphene oxide (GO) of 0.15mg/mL
(TPPyP), the UV, visible light-absorption spectrum obtained under different GO additions, in figure, Far Left from below to up, GO additions by
Step increases, wherein, abscissa represents wavelength, and ordinate represents absorbance.
Fig. 2 is variation relation curve of the maximum absorption band wavelength change (Δ λ) with addition GO volumes, and abscissa represents GO's
Volume is added in, ordinate represents maximum absorption band wavelength change.
Fig. 3 be (1) pure TPPyP aqueous solutions, (2) TPPyP/GO with three kinds of compounds, (3) TPPyP/CCG-1, (4)
The UV, visible light of TPPyP/CCG-2-absorption spectrum correlation curve, wherein, abscissa represents wavelength, and ordinate represents absorbance,
Fig. 4 is (2) TPPyP/GO of three kinds of compounds, and (3) TPPyP/CCG-1, Δ λ when (4) TPPyP/CCG-2 reaches stable compare
Figure, abscissa represent substance number, maximum absorption band wavelength change when ordinate expression reaches stable.
Fig. 5 be TPPyP, TPPyP/CCG-2, TPPyP/GO and TPPyP/CCG-1 respectively with Zn2+Mechanism is at any time
The relational graph that the maximum absorption wavelength (Δ λ) of the uv-visible absorption spectra of variation changes over time, abscissa represent the time,
Ordinate represents maximum absorption band wavelength change.
Fig. 6 be TPPyP, TPPyP/GO, TPPyP/CCG-1 and TPPyP/CCG-2 respectively with Pb2+,Ca2+,Cd2+,Cu2+,
Fe2+,Hg2+,K+,Mg2+,Mn2+,Ni2+,Zn2+Figure is compared in characteristic peak red shift (Δ λ) after Action of Metal Ions, and abscissa represents
Substance is numbered, and ordinate represents maximum absorption band wavelength change.
Fig. 7 is (A) CCG-2, (B) TPPyP/CCG-2, (C) TPPyP-Zn2+The atomic force microscope of/CCG-2 compounds
(AFM) phenogram, abscissa represent the spacing of white straight line starting point to the end in figure, and ordinate indicates straight line by White curves
On height distribution.
Fig. 8 is (A) CCG-2, (B) TPPyP-Zn2+/ CCG-2 composite materials visible ray photograph under degradation p-nitrophenol with
The change curve of time, abscissa represent degradation time, and ordinate represents degradation rate.
Fig. 9 is (A) TPPyP-Zn2+/CCG, (B) TPPyP/CCG, (C) TPPyP composite materials are in the visible ray portion of xenon lamp
Divide (λ>Photoelectricity flow graph 400nm), abscissa represent the time, and ordinate represents current strength.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described in further detail the present invention.
Embodiment 1
Take bromination four (N- pyridylpropyls) porphyrin (TPPyP) the drying solid powder synthesized by classical Alder-longer methods
TPPyP aqueous solutions are prepared at end；Graphene oxide (GO) is prepared, ultrasonic disperse is prepared into the GO aqueous dispersions of 0.15mg/mL, amount
It takes 40mL, adds in 28% ammonium hydroxide 72 μ L, 80% hydrazine hydrate, 1.8 μ L (or 7.5 μ L), 95 DEG C of reaction 1h, reaction postcooling to room temperature,
GO, CCG-1, CCG-2 are respectively designated as by reducing degree difference.The preparation of compound is monitored by uv-visible absorption spectra
Process, test equipment are Shimadzu UV-2501PC uv-visible absorption spectra instrument.
The results are shown in Figure 1, adds in the GO aqueous dispersions of 0.15mg/mL under room temperature into 1 μM of TPPyP aqueous solution, is located at
The porphyrin characteristic peak (Soret bands) of 423nm continuously decreases, with gradually increasing for GO additions, the characteristic peak of complex solution
Gradual red shift, maximum absorption wavelength reaches and stabilizes to 435nm (Δ λ=13nm) to get TPPyP/GO when the amount of GO is 50 μ L
Compound.Fig. 2 is maximum absorption band wavelength change (Δ λ) with the variation relation curve for adding in GO volumes.
Prepare TPPyP/CCG-1, TPPyP/CCG-2 compound respectively by similar approach, the results are shown in Figure 3.From figure
As can be seen that from sample TPPyP/GO to TPPyP/CCG-2, with the increase of graphene oxide reducing degree, TPPyP exists
Red shift occurs with corresponding absorption peak with porphyrin feature Soret at 423nm, compound can determine whether by the Δ λ for reaching stable
Formation, the movement of characteristic peak maximum is respectively 24nm and 32nm, this shows to have occurred between porphyrin and three kinds of graphenes effective
Non-covalent self assembly recombination process.Fig. 4 is that Δ λ when reaching stable compares figure.
Embodiment 2
Three kinds of compounds (GO/TPPyP, TPPyP/CCG-1, TPPyP/CCG-2) are prepared, then divide by step in embodiment 1
A concentration of 2 μM of configuration metal ions Zns are not added dropwise2+Aqueous solution makes concentration proportioning reach 1:2, at room temperature mixing stand, by it is ultraviolet-can
See the variation of absorption spectrum monitoring compound and characteristic absorption peak before and after metallic ion coordination.
The results are shown in Figure 5, with Zn2+For exemplary ion, it and GO/TPPyP, TPPyP/CCG-1 and TPPyP/ are confirmed
The ultraviolet-visible absorption spectroscopy of CCG-2 interaction different times.Due to matching for Porphyrin Molecule under usual conditions and metal ion
Position process kinetics energy barrier is higher, needs to realize coordination by heating or other auxiliary reagents.Such as Fig. 5, pure TPPyP under room temperature
With Zn2+It is difficult to directly be coordinated, characteristic peak has not yet to see apparent motion after mixing 48h, needs heating condition or flows back for a long time anti-
It should could occur.However, other the three kinds TPPyP molecules and Zn for being compounded with graphene2+Can at room temperature (25 degrees Celsius) hair
Raw apparent interaction shows as compound Soret bands and extends gradually generation red shift at any time, this illustrates that metal ion enters porphin
Coordination has occurred with compound in quinoline ring.Comparative result is it is found that TPPyP/GO reaches stable, and red shift in 80min or so
24nm；TPPyP/CCG-1 (40min), TPPyP/CCG-2 (25min) speed of action faster, and red shift become apparent (be respectively
37nm, 47nm).Therefore, the above results explanation：In the range of we study, with the reducing degree of graphene oxide
Increase, compound and Zn2+Combination speed accelerate.This also illustrates that the graphene oxide using gradient reduction can regulate and control TPPyP
The different degrees of planarization of molecule, it is effective to tune TPPyP and Zn2+The coordination ability of ion, so as to successfully realize room temperature condition
It is prepared by the green of lower metalloporphyrin-graphene nanocomposite material.
Embodiment 3
Compound GO/TPPyP, TPPyP/CCG-1, TPPyP/CCG-2 are prepared, then be added dropwise respectively by step in embodiment 1
Other metal ion Pb2+,Ca2+,Cd2+,Cu2+,Fe2+,Hg2+,K+,Mg2+,Mn2+,Ni2+, with the spy of uv-visible absorption spectra
Sign peak red shift (Δ λ) compares figure.
The results are shown in Figure 6, the results showed that by three kinds of GO/TPPyP, TPPyP/CCG-1, TPPyP/CCG-2 points of compounds
Not and Pb2+,Ca2+,Cd2+,Cu2+,Fe2+,Hg2+,K+,Mg2+,Mn2+,Ni+,Zn2+11 metal ion species interact, while with
TPPyP is compared, and compares the situation of movement of porphyrin and Soret bands after metal coordination.Compound GO/TPPyP as shown in Figure 6A
To Cd2+、Hg2+、Zn2+There is obvious response；Compound TPPyP/CCG-1 is to Pb2+,Cd2+,Hg2+,Mn2+,Zn2+All have compared with
Strong interaction, such as Fig. 6 B；For compound TPPyP/CCG-2, Cd2+、Zn2+Response it is stronger, Pb2+、Hg2+Response become
Weak, the response of other ions is also slightly strengthened, such as Fig. 6 C.Therefore, this result further illustrates that we can utilize gradient to restore
Graphene oxide cause the different degrees of planarization of TPPyP molecules, the effective coordination for tuning TPPyP and different metal ions
Ability, so as to prepared by the green for successfully realizing series metal porphyrin-graphene nanocomposite material under room temperature.
Embodiment 4
With (A) CCG-2 prepared in above-described embodiment 2, (B) TPPyP/CCG-2, (C) TPPyP-Zn2+/ CCG-2 is representative
The pattern and thickness distribution of sample test graphene nanocomposite material sample.
The instrument specifically tested is：Bruker DimensionPT atomic force microscope, test substrate are the cloud newly cleaved
Master slice, test temperature are 25 DEG C.As shown in Figure 7, the results showed that：The thickness of the pure graphene of monolithic (CCG-2) is about 1.3nm, table
The thickness that face is compounded with the graphene complex (TPPyP/CCG-2) of porphyrin is about 5.1nm, it is thus identified that Porphyrin Molecule is in CCG tables
The non-covalent self assembly in face；Compound TPPyP-Zn2+The thickness of/CCG-2 is about 4.8nm, Zn2+Inside embedded porphyrin ring, into one
Step increases the planarization degree of porphyrin, and thickness slightly reduces, also confirmed to be embedded in Zn2+TPPyP Porphyrin Molecules still retain
On CCG surfaces, stable ternary graphene composite material is formd at normal temperatures.
Embodiment 5
Compound TPPyP-Zn is prepared by step in embodiment 22+/ CCG-2 and CCG-2, photocatalytic degradation is to nitro respectively
Phenol (4-NP).The 4-NP of 250 μ L is added in into 25mL complex catalysts, first secretly 20min is stirred in absorption in light protected environment,
Then in the visible light part (λ of xenon lamp>400nm) photocatalytic degradation samples every 20min, adds in 20 μ L 0.2M's later
NaOH solution, the absorbance change value that the characteristic peak of 4-NP at 400nm is located at using the detection of uv-visible absorption spectra instrument are calculated
Its degradation efficiency.
The results are shown in Figure 8, compound TPPyP-Zn2+/ CCG-2 is substantially higher in CCG the degradation efficiency of 4-NP, in light
Catalytic degradation phenol wastewater field has a good application prospect.
Embodiment 6
Compound (A) TPPyP-Zn is prepared by step in embodiment 22+/ CCG-2, (B) TPPyP/CCG-2, (C) TPPyP are surveyed
Try the photoelectric properties of graphene nanocomposite material.
The present embodiment uses three-electrode system, is ginseng by compound drop coating to ITO surfaces preparation work electrode, calomel electrode
It is to electrode than electrode, platinum electrode, light source is the visible light part (λ in xenon lamp>400nm), in the Na2SO of 0.1M3Electrolysis
The photoelectric properties of graphene nanocomposite material are tested in matter solution.
The results are shown in Figure 9, compound (A) TPPyP-Zn2+The photoelectric current of/CCG-2 to be apparently higher than (B) TPPyP/CCG,
(C) TPPyP has potential application value in field of photovoltaic materials.
Above-described embodiment be used for illustrate the present invention rather than limit the invention, the present invention spirit and
In scope of the claims, to any modifications and changes that the present invention is made, protection scope of the present invention is both fallen within.
Claims (3)
1. a kind of method for preparing metalloporphyrin-graphene nanocomposite material under room temperature, includes the following steps：
（1）Certain density cationic porphyrin aqueous solution is configured, the graphene oxide dispersion of gradient reduction is added dropwise thereto
Liquid is monitored by uv-visible absorption spectra, when reaching stable red shift just, obtains porphyrin-graphene complex；Described
Gradient restores：With 40 mL, on the basis of 0.15 mg/mL graphene oxide dispersions, the 80 of 0-10 μ L is added dropwise thereto
% hydrazine hydrate solutions, the graphene oxide dispersion after being restored；
（2）Certain density aqueous metallic ions are added dropwise into above-mentioned porphyrin-graphene complex dispersion liquid so that compound
In porphyrin acted on metal ion in room temperature or at room temperature, monitored by uv-visible absorption spectra, when reaching stable red shift
When to get to metalloporphyrin-graphene nanocomposite material, general structure is as follows：
Wherein substituent R is CH3, CH2CH3,(CH2)2CH3, (CH2)3CH3, (CH2)4CH3, (CH2)5CH3, (CH2)3OH,
CH2COOCH2CH3, CH2C6H5, CH2C6H4CH3And CH2C6H4NO2In one kind；
Wherein M is Zn2+, Cd2+, Pb2+Or Hg2+。
2. the method as described in claim 1 for preparing metalloporphyrin-graphene nanocomposite material under room temperature, described
Cationic porphyrin recycles the alkylated reaction synthesis of N after synthesizing four pyridylporphyrins by Alder-longo methods or directly purchases
It buys；A concentration of 1 ~ 100 μm of ol/L of the cationic porphyrin solution.
3. the method as described in claim 1 for preparing metalloporphyrin-graphene nanocomposite material under room temperature, step
（2）In, the ratio between substance withdrawl syndrome of porphyrin-graphene complex and metal ion is 1:1~5.
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| US11079371B2 (en) | 2018-02-20 | 2021-08-03 | Boston Scientific Scimed, Inc. | Chemical sensors with non-covalent surface modification of graphene |
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| CN108918629B (en) * | 2018-09-21 | 2020-06-05 | 浙江理工大学 | Preparation method of copper-graphene quantum dot co-supported porphyrin nanosheet modified electrode |
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